US3696047A - Chemical reducing agents of enhanced hydrocarbon solubility - Google Patents
Chemical reducing agents of enhanced hydrocarbon solubility Download PDFInfo
- Publication number
- US3696047A US3696047A US81164A US3696047DA US3696047A US 3696047 A US3696047 A US 3696047A US 81164 A US81164 A US 81164A US 3696047D A US3696047D A US 3696047DA US 3696047 A US3696047 A US 3696047A
- Authority
- US
- United States
- Prior art keywords
- dihydride
- alkali metal
- hydrocarbon
- lewis base
- metal aluminum
- 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
Links
- 229930195733 hydrocarbon Natural products 0.000 title abstract description 38
- 150000002430 hydrocarbons Chemical class 0.000 title abstract description 38
- 239000004215 Carbon black (E152) Substances 0.000 title abstract description 33
- 239000003638 chemical reducing agent Substances 0.000 title abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 41
- 150000001340 alkali metals Chemical class 0.000 abstract description 41
- 229910052782 aluminium Inorganic materials 0.000 abstract description 40
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 40
- 239000002879 Lewis base Substances 0.000 description 42
- 150000007527 lewis bases Chemical class 0.000 description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 150000003512 tertiary amines Chemical class 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 150000002170 ethers Chemical class 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 150000004996 alkyl benzenes Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- -1 tertiary amine Chemical class 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003738 xylenes Chemical class 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical group [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 150000003003 phosphines Chemical group 0.000 description 2
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical group [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical class CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical class [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002633 crown compound Substances 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- 150000005195 diethylbenzenes Chemical class 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- YQYUUNRAPYPAPC-UHFFFAOYSA-N n,n-diethyl-2-methylaniline Chemical compound CCN(CC)C1=CC=CC=C1C YQYUUNRAPYPAPC-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000002932 p-cymene derivatives Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical class CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/065—Aluminium compounds with C-aluminium linkage compounds with an Al-H linkage
Definitions
- Alkali metal aluminum dialkyl dihydrides have been suggested for use as reducing agents (Ziegler et al. US. 2,915,541; 3,143,542). Unfortunately, however, the hydrocarbon solubility of these compounds, especially the sodium aluminum dialkyl dihydrides, is not as high as one might wish. For example, high purity sodium aluminum diethyl dihydride is virtually insoluble in parafiinic hydrocarbons although it is soluble to some extent in aromatic hydrocarbons. In my prior copending application Ser. No. 79,682 (Case 3558, executed by me on Oct. 8, 1970), filed Oct. 9, 1970 and entitled Chemical Reducing Agent it has been pointed out that sodium aluminum diethyl dihydride is more soluble and more stable in liquid alkyl benzenes than it is in benzene.
- the hydrocarbon solubility of alkali metal aluminum dialkyl dihydrides is increased by including in the solution a small quantity of an innocuous hydrocarbon-soluble Lewis base such as tertiary amine, an ether, or the like.
- an innocuous hydrocarbon-soluble Lewis base such as tertiary amine, an ether, or the like.
- the presence in the system of the small quantity of Lewis base significantly increases the solubility of the alkali metal aluminum dialkyl dihydride in all types of hydrocarbon solventsi.e., parafiins, cycloparafiins, and aromatics.
- this invention enables the provision of more concentrated reagent solutions of the alkali metal aluminum dialkyl dihydrides. Under normal conditions, the solutions may be stored, transported and used without incurring phase separatione.g., formation of sediments or precipitates. Further, excessive shipping costs for the reducing agent solutions may be avoided. In handling the reagent solutions, ordinary precautions should be observed such as avoiding exposure to flames or excessive exposure to
- One embodiment of this invention provides a process of increasing the solubility of an alkali metal aluminum dialkyl dihydride in a hydrocarbon solvent which comprises including in the solution a small quantity of an innocuous hydrocarbon-soluble Lewis base.
- this invention provides a liquid hydrocarbon having dissolved therein an alkali metal aluminum dialkyl dihydride and a small amount of an innocuous hydrocarbon-soluble Lewis base.
- the alkali metal aluminum dialkyl dihydrides involved in the present invention include those in which the alkali metal constituent is lithium, sodium, potassium, rubidium, or cesium. However, the invention is most preferably applied to the sodium aluminum dialkyl dihydrides, especially those having up to about 4 carbon atoms in each alkyl group as these compounds are among the most effective reducing agents of the class and can be prepared from relatively inexpensive and readily available raw materials.
- Exemplary alkali metal aluminum dialkyl dihydrides to which this invention may be applied include lithium aluminum dimethyl dihydride, lithium aluminum diethyl d hydride, lithium aluminum dibutyl dihydride, sodium aluminum dipentyl dihydride, sodium aluminum dihexyl dihydride, sodium aluminum dioctyl dihydride, potassium aluminum diethyl dihydride, potassium aluminum diisobutyl dihydride, potassium aluminum dihexyl dihydride, rubidium aluminum didodecyl dihydride, cesium aluminum dioctadecyl dihydride, and the like.
- the preferred sodium compounds are sodium aluminum dimethyl dihydride, sodium aluminum diethyl dihydride, sodium aluminum dipropyl dihydride, sodium aluminum dibutyl dihydride and sodium aluminum diisobutyl dihydride.
- paraffinic hydrocarbons such as pentane, hexane
- solvents should have freezing points below about 15 C. and more preferably below 0 C.i.e., they should exist in the liquid state of aggregation under average room temperature conditions.
- the preferred solvents are alkyl benzenes as these confer enhanced stability to the system.
- the use of toluene or xylene (the ortho, meta, or para isomers; or mixed isomers) is particularly preferred as the resultant solutions have good thermal stability and handling properties, and the solvents are relatively inexpensive and readily available.
- the solubility of alkali metal aluminum dialkyl dihydrides in hydrocarbons will vary depending upon such factors as the identity of the alkali metal aluminum dialkyl dihydride, the identity of the hydrocarbon solvent and the temperature of the system.
- a feature of this invention is that even where the solubility of the alkali metal aluminum dialkyl dihydride in a given hydrocarbon is substantial under a given set of conditions, the inclusion in the the system of a small quantity of an innocuous hydrocarbon-soluble Lewis base will improve the solubility so that under a different set of conditions (e.g., reduction in temperature) there will be a reduced tendency for separation of the alkali metal aluminum dialkyl dihydride to occur.
- the invention is most preferably applied however to systems wherein the solubility of the alkali metal aluminum dialkyl dihydride in the hydrocarbon at 25 C. does not exceed about 30 weight percent in the absence of the Lewis base component.
- Lewis bases are available for use in practicing this invention. The only requirements are that the Lewis base be hydrocarbon-soluble and that it be innocuous in the sense that it may form a soluble complex with the alkali metal aluminum dialkyl dihydride and it may dissociate associated molecules of the alkali metal aluminum dialkyl dihydride but it otherwise is non-reactive therewith. It is postulated that the Lewis base may function toincrease the hydrocarbon solubility of alkali metal aluminum dialkyl dihydrides by causing dissociation or breakdown of associated molecules of the alkali metal aluminum dialkyl dihydride.
- the invention requires only the incorporation in the system of a small amount of an innocuous hydrocarbon-soluble Lewis base to achieve the desired result.
- the innocuous Lewis bases which are used in the practice of this invention are compounds which contain no functionality that would adversely react with the alkali metal aluminum dialkyl dihydride at temperatures under which the hydride will be put to its intended use.
- the Lewis base will not contain reducible non-aromatic unsaturated nor such reducible functional groups as hydroxyl, sulfhydryl, carbonyl, carboxyl, peroxy, or like groups.
- Lewis bases which are suitable for the practice of this invention include ethers, tertiary amines, tertiary phosphines, tertiary arsines, tertiary stibines, and other organic Lewis bases having the character and attributes referred to above. From the cost elfectiveness standpoint the use of tertiary amines and ethers is preferred.
- Exemplary Lewis bases include tertiary hydrocarbyl amines (aliphatic, aromatic, or heterocyclic) such as trimethyl amine, triethyl amine, tributyl amine, N,N-dimethyl aniline, pyridine, N-methyl piperidine, N,N,N',N'- tetramethylethylenediamine, triethylene diamine, N,N-diethyltoluidine, N,N-dimethyl piperazine, triphenyl amine, and other tertiary amine bases found in any appropriate text book of organic chemistry; and hydrocarbyl ethers such as diethyl ether, dibutyl ether, the dimethyl ether of ethylene glycol, the diethyl ether of ethylene glycol, trimethylol propane, the dimethyl ether of diethylene glycol, the diethyl ether of diethylene glycol, the dibutyl ether of diethylene glycol, the dimethyl ether of tetramethylene glyco
- ethers such as tetrahydrofuran and alkyl substituted tetrahydrofurans are particularly convenient, effective and relatively inexpensive, and thus their use constitutes a preferred embodiment of this invention.
- Exemplary tertiary hydrocarbyl phosphines include triethyl phosphine, tributyl phosphine, triphenyl phosphine, tricyclohexyl phosphine, and other analogous compounds.
- the corresponding trihydrocarbyl derivatives of arsenic and antimony are also suitable as are other innocuous hydrocarbon-soluble Lewis bases.
- the suitability of any given Lewis base for use in the practice of this invention can be readily ascertained by the simple expedient of performing a few laboratory tests. Given the teachings of this invention one skilled in the art should have no difficulty in finding numerous and sundry suitable Lewis bases whether or not they are specifically referred to herein.
- the proportions of the Lewis base may be varied to suit the needs of the occasion the solution of the alkali metal aluminum dialkyl dihydride in a hydrocarbon solvent will usually contain from about 0.5 to about percent, and preferably from about 0.5 to about 5 percent, by weight of the Lewis base.
- concentrations in the finished solution ranging from about 0.5 to about 1.5 percent by weight based on the total weight of solution are found especially advantageous.
- Sodium aluminum diisobuty] dihydride normally has a solubility in toluene at room temperature of about 5 to 6 percent by weight. However incorporation in the solution of 5 percent of tetrahydrofiuran based on the total weight of the solution increases the solubility so that the solution may contain as much as 22 percent by weight of sodium aluminum diisobutyl dihydride.
- EXAMPLE HI At 25 C. the solubility of sodium aluminum diethyl dihydride in mixed xylene isomers enables the preparation of solutions containing approximately 26 weight percent of the hydride. However when the solution also contains tetrahydrofuran (one percent based on the total weight of the solution) it is possible to provide solutions containing at least as much as 41 percent by weight of the sodium aluminum diethyl dihydride.
- a process of increasing the solubility of an alkali metal aluminum dialkyl dihydride in a hydrocarbon solvent which comprises including in the solution a small quantity in the range of from about 0.5 to about 10 percent by weight of an innocuous hydrocarbon-soluble organic Lewis base, innocuous in the sense that it may form a soluble complex with the alkali metal aluminum dialkyl dihydride and it may dissociate associated molecules of the alkali metal aluminum dialkyl dihydride but it otherwise is non-reactive therewith.
- alkali metal aluminum dialkyl dihydride is a sodium aluminum dialkyl dihydride.
- hydrocarbon solvent is a liquid mononuclear aromatic hydrocarbon
- the alkali metal aluminum dialkyl dihydride is a sodium aluminum dialkyl dihydride
- the Lewis base is a tertiary amine
- hydrocarbon solvent is a liquid mononuclear aromatic hydrocarbon
- alkali metal aluminum dialkyl dihydride is a sodium aluminum dialkyl dihydride
- Lewis base is a monoether
- composition of claim 11 wherein the hydrocarbon is a liquid aromatic hydrocarbon, wherein the alkali metal aluminum dialkyl dihydride is a sodium aluminum dialkyl dihydride having up to about 4 carbon atoms in each alkyl group and wherein the Lewis base is an ether.
- composition of claim 13 wherein the hydrocarbon is a liquid aromatic hydrocarbon, wherein the alkali metal aluminum dialkyl dihydride is a sodium aluminum dialkyl dihydride having up to about 4 carbon atoms in each alkyl group and wherein the Lewis base is a cyclic monoether.
- composition of claim 11 wherein the hydrocarbon is toluene or xylene, wherein the alkali metal aluminum dialkyl dihydride is sodium aluminum diethyl dihydride and wherein the Lewis base is tetrahydrofuran present in an amount of from about 0.5 to about 5 percent by weight based on the total weight of the solution.
- composition of claim 11 wherein the hydrocarbon is a mixture of xylene isomers, wherein the alkali metal aluminum dialkyl dihydride is sodium aluminum diethyl dihydride and wherein the Lewis base is tetrahydrofuran present in an amount of from about 0.5 to about 1.5 percent by weight based on the total weight of the solution, the sodium aluminum diethyl dihydride being present in an amount of at least about 25 percent by weight based on the total weight of the solution.
- composition of claim 11 wherein the hydrocarbon is toluene, wherein the alkali metal aluminum dialkyl dihydride is sodium aluminum diethyl dihydride and wherein the Lewis base is tetrahydrofuran present in an amount of from about 0.5 to about 1.5 percent by weight based on the total weight of the solution, the sodium aluminum diethyl dihydride being present in an amount of at least about 15 percent by weight based on the total weight of the solution.
- Lewis base is selected from the group consisting of ethers, tertiary amines tertiary phosphines, tertiary arsines, and tertiary stibines.
- the hydrocarbon solvent is a liquid mononuclear aromatic hydrocarbon
- the alkali metal aluminum dialkyl dihydride is a sodium aluminum dialkyl dihydride in which each alkyl group contains from 1 to 4 carbon atoms and wherein said Lewis base is an ether employed in an amount ranging from about 0.5 to about 5 perecnt by weight of the solution.
- composition of claim 11 wherein said Lewis base is tetrahydrofuran or alkyl substituted tetrahydrofuran present in an amount ranging from about 0.5 to about 5 percent by weight based on the total weight of the solution.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8116470A | 1970-10-15 | 1970-10-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3696047A true US3696047A (en) | 1972-10-03 |
Family
ID=22162493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US81164A Expired - Lifetime US3696047A (en) | 1970-10-15 | 1970-10-15 | Chemical reducing agents of enhanced hydrocarbon solubility |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3696047A (de) |
| JP (1) | JPS5133891B1 (de) |
| BE (1) | BE773960A (de) |
| CH (1) | CH560720A5 (de) |
| DE (2) | DE2166183B2 (de) |
| FR (1) | FR2111392A5 (de) |
| GB (1) | GB1344680A (de) |
| NL (1) | NL150799B (de) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4174449A (en) * | 1977-06-15 | 1979-11-13 | Jacques Bourrelly | Process for the reduction of quinidinone to quinidine |
| US4698437A (en) * | 1985-04-20 | 1987-10-06 | Schering Aktiengesellschaft | Alkali metal dialkylaluminum dihydrides and solutions thereof in aromatic hydrocarbons |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5589434U (de) * | 1978-12-14 | 1980-06-20 | ||
| EP3871532A4 (de) | 2018-10-26 | 2022-11-09 | Japan Tobacco Inc. | Gehäuse und aromaansauger damit |
-
1970
- 1970-10-15 US US81164A patent/US3696047A/en not_active Expired - Lifetime
-
1971
- 1971-10-14 NL NL717114169A patent/NL150799B/xx not_active IP Right Cessation
- 1971-10-14 BE BE773960A patent/BE773960A/xx not_active IP Right Cessation
- 1971-10-14 FR FR7136990A patent/FR2111392A5/fr not_active Expired
- 1971-10-15 CH CH1503271A patent/CH560720A5/xx not_active IP Right Cessation
- 1971-10-15 JP JP46081032A patent/JPS5133891B1/ja active Pending
- 1971-10-15 GB GB4804371A patent/GB1344680A/en not_active Expired
- 1971-10-15 DE DE19712166183 patent/DE2166183B2/de not_active Ceased
- 1971-10-15 DE DE2151495A patent/DE2151495C3/de not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4174449A (en) * | 1977-06-15 | 1979-11-13 | Jacques Bourrelly | Process for the reduction of quinidinone to quinidine |
| US4698437A (en) * | 1985-04-20 | 1987-10-06 | Schering Aktiengesellschaft | Alkali metal dialkylaluminum dihydrides and solutions thereof in aromatic hydrocarbons |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2166183A1 (de) | 1973-06-20 |
| JPS5133891B1 (de) | 1976-09-22 |
| FR2111392A5 (de) | 1972-06-02 |
| CH560720A5 (de) | 1975-04-15 |
| DE2166183B2 (de) | 1977-03-10 |
| DE2151495C3 (de) | 1973-10-04 |
| BE773960A (fr) | 1972-04-14 |
| DE2151495B2 (de) | 1973-02-15 |
| DE2151495A1 (de) | 1972-04-20 |
| NL150799B (nl) | 1976-09-15 |
| NL7114169A (de) | 1972-04-18 |
| GB1344680A (en) | 1974-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| ES229711A1 (es) | UN MÉTODO DE POLIMERIZAR, POR LO MENOS, UN HIDROCARBURO NO SATURADO QUE CONTIENE UN GRUPO VINiLICO | |
| GB1011979A (en) | Production of epitaxial films | |
| Vinal et al. | The Reduction of Nickel (II) Halides by Trialkyl Phosphites | |
| US3696047A (en) | Chemical reducing agents of enhanced hydrocarbon solubility | |
| Fenby et al. | Heats of mixing of nonelectrolyte solutions. IV. Mixtures of fluorinated benzenes | |
| ES398384A1 (es) | Un procedimiento para la preparacion de una sal de poliami-na o una mezcla que contiene dicha sal. | |
| GB857882A (en) | Compounds containing boron and silicon | |
| ES421760A1 (es) | Un procedimiento para preparar una mezcla de hidrocarbila- minas de alto y de bajo peso molecular. | |
| US3103537A (en) | Boron compounds | |
| Yamamoto et al. | Structure and reactivity of organic ions in gas-phase radiolysis. I. The C7H7+ ion from toluene, ethylbenzene, and m-xylene | |
| Sommer et al. | Racemization of an Optically Active Fluorosilane without Displacement of Fluoride Ion: Evidence for an Expanded-Octet Mechanism | |
| US2893857A (en) | Aminolead compound and herbicidal composition containing same | |
| Bent | Hybridization and bond properties Effects of second-order hybridization on the σ-bonds in thionyl, sulphuryl, phosphorus, phosphoryl and thiophosphoryl halides | |
| Gibbons et al. | The Partial Hydrolysis of Dialkyltin Dihalides | |
| US2924579A (en) | Method of preparing aluminum chloride complex catalyst | |
| Weinkam et al. | Hydrolysis, methanolysis and ammonolysis of dicarboxylic acids and methyl esters under conditions of chemical ionization mass spectrometry | |
| US3088957A (en) | Method for separating organolead compounds | |
| US2927935A (en) | Preparation of cyclopentadienyl manganese tricarbonyl compounds | |
| US3038916A (en) | Thermal stabilization of alkyllead compounds | |
| US2870095A (en) | Liquid gelling agent | |
| Ashida et al. | The crystal structures of ethylenediammonium chloride and tetramethylenediammonium chloride | |
| US3637885A (en) | Separation of aluminum alkyls from olefins | |
| US3008988A (en) | Synthesis of borazoles | |
| US3088962A (en) | Acetylenic nickel compounds | |
| US3511879A (en) | Cyclobutene imines and allene amidines and preparation thereof |