USH919H - Process for producing polyamine boranes - Google Patents
Process for producing polyamine boranes Download PDFInfo
- Publication number
- USH919H USH919H US07/388,540 US38854089A USH919H US H919 H USH919 H US H919H US 38854089 A US38854089 A US 38854089A US H919 H USH919 H US H919H
- Authority
- US
- United States
- Prior art keywords
- water
- triethylenediamine
- reaction
- amine
- acid
- 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.)
- Abandoned
Links
- 229910000085 borane Inorganic materials 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 28
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims description 45
- 229920000768 polyamine Polymers 0.000 title claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 19
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 8
- 239000011707 mineral Substances 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 26
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- -1 amine boranes Chemical class 0.000 claims description 16
- 150000003512 tertiary amines Chemical class 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical class NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims description 2
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical class CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 4
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000003916 ethylene diamine group Chemical group 0.000 claims 1
- 239000012429 reaction media Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 125000004427 diamine group Chemical group 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229960000583 acetic acid Drugs 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229960004132 diethyl ether Drugs 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000011027 product recovery Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 125000005270 trialkylamine group Chemical group 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 229940093499 ethyl acetate Drugs 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DDPRYTUJYNYJKV-UHFFFAOYSA-N 1,4-diethylpiperazine Chemical compound CCN1CCN(CC)CC1 DDPRYTUJYNYJKV-UHFFFAOYSA-N 0.000 description 1
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical compound C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- KKAXNAVSOBXHTE-UHFFFAOYSA-N boranamine Chemical class NB KKAXNAVSOBXHTE-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- RJFWUOJTSKNRHN-UHFFFAOYSA-N borane;pyridine Chemical class B.C1=CC=NC=C1 RJFWUOJTSKNRHN-UHFFFAOYSA-N 0.000 description 1
- NNTOJPXOCKCMKR-UHFFFAOYSA-N boron;pyridine Chemical compound [B].C1=CC=NC=C1 NNTOJPXOCKCMKR-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000012733 comparative method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- 239000012971 dimethylpiperazine Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005891 transamination reaction Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- 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
Definitions
- This invention relates to a process for producing tertiary polyamine boranes by the reaction of a borohydride with a tertiary polyamine.
- Tertiary amine boranes are utilized in many fields, which include the preparation of epoxy resins by acting as a curing agent or accelerators; in organic synthesis as reducing agent; as a reagent for the hydroboration of alkenes and in electroless plating applications. Essentially five methods have been developed for the synthesis of tertiary amine-boranes and these methods are described as follows:
- U.S. Pat. No. 3,013,016 discloses a process embraced within synthesis route 5 for producing trialkylamine boranes.
- a trialkylamine e.g. trimethylamine or triethylamine
- potassium borohydride in the presence of an aqueous phase containing an inert organic solvent which is immiscible or only partially miscible with water.
- Carbon dioxide, or an acid source such as a carboxylic acid or mineral acid is added to the reaction medium. Reaction occurs at about 20°-40° C. and atmospheric pressure.
- the product is recovered by separating the organic solution containing the trialkylamine borane for the aqueous phase and then separating the organic solvent from the trialkylamine borane by distillation.
- Czechoslovakian patent 242,064 discloses a process for producing tertiary amine-boranes via synthesis route 5 wherein an anhydrous suspension of a metal tetrahydroborate and tertiary amine in an organic solvent is contacted with carbon dioxide gas at temperatures ranging from about 0° to 50° C. for a period of 1-5 hours. The reaction product is washed with water, dried and the solvent evaporated.
- British patent 909,390 discloses a process for producing amine boranes by reacting an amine salt with aqueous metal borohydride in organic solvent at room temperature under neutral or alkaline conditions. Product recovery is accomplished by separating the amine borane as it is formed by separating organic solvent containing the amine borane from the aqueous layer and then distilling the solvent from the amine borane.
- Taylor, et al. in J. Am. Chem. Soc., vol. 77, 1955, pp. 1506-7 disclose the production of pyridine-borane complexes by reacting pyridine hydrochloride with sodium borohydride in the presence of pyridine solvent. Byproduct sodium chloride precipitates and unreacted pyridine hydrochloride is precipitated by the addition of ether. Unreacted pyridine is separated from the pyridine-borane reaction product by distillation.
- This invention relates to an improved process for preparing amine boranes by the reaction of a metal borohydride with a tertiary amine in the presence of an inert, water immiscible organic solvent and a protic acid source.
- the improvement for enhancing yields in the production of the amine borane complexes having a water solubility greater than about 2 grams per 100 cc's at 25° C. and where the amine is a polyamine containing at least one tertiary nitrogen atom comprises effecting the reaction of the borohydride with the complex in the presence of water, wherein the water is present in a small but catalytically effective amount but insufficient for forming two phases.
- a tertiary amine or salt is reacted with a borohydride under modest reaction conditions.
- the tertiary amines are polyamines containing a tertiary nitrogen atom, e.g., diamines having from about 2-10 carbon atoms, which may be aliphatic or cyclic.
- Examples of tertiary amines include N-alkylated polyamines, e.g.
- methylated and ethylated derivatives of polyamines such as, ethylenediamine, propylenediamine, diethylenetriamine and triethylenetetraamine, e.g., methylated ethylenediamine or methylated propanediamine and methylated triethylenetetramine; cyclic amines, e.g. dimethylpiperazine, diethylpiperazine, triethylenediamine and methyltriethylenediamine; and ether amines, e.g., dimethylaminoethyl ether and bis morpholinoethyl ether.
- polyamines such as, ethylenediamine, propylenediamine, diethylenetriamine and triethylenetetraamine, e.g., methylated ethylenediamine or methylated propanediamine and methylated triethylenetetramine
- cyclic amines e.g. dimethylpiperazine, diethylpiperazine, triethylenediamine and methyl
- the borohydrides which are reacted with the tertiary amine include alkali metal borohydrides such as sodium borohydride and potassium borohydride and lithium borohydride. Borane may also be used.
- organic solvent which is inert to the reaction medium.
- organic solvents which are suited for producing tertiary amine boranes include hydrocarbons such as benzene, toluene, xylene; ethers such as diethylether, methodyethylether, dimethoxyethane, methyltert-butylether, dioxane, tetrahydrofuran and isopropyl ether; aliphatic hydrocarbons, i.e., those having from about 6 to 20 carbon atoms, e.g., hexane, pentane, dodecane, and the like.
- carboxylic esters such as ethylacetate, propylacetate and the like and nitriles such as acetonitrile can be used.
- the organic solvents used in the synthesis are well known and most will work so long as the reactant amine and product borane complex are soluble in the solvent and sufficiently volatile such that they can be distilled away from the reaction product.
- the reaction of the tertiary amine with the alkali metal borohydride is carried out in the presence of a protic acid source, e.g. a C 2-10 , preferably a C 2 -C 4 carboxylic acid, or an anhydrous mineral acid.
- a protic acid source e.g. a C 2-10 , preferably a C 2 -C 4 carboxylic acid, or an anhydrous mineral acid.
- C 2-10 carboyxlic acid sources include, acetic acid, propionic acid, butyric acid and examples of mineral acids include hydrochloric, phosphoric and sulfuric acids.
- mineral acid it may be necessary to dilute such acids in an organic solvent as the anhydrous, concentrated mineral acids may be too strong and cause product decomposition.
- the reaction is carried out in the presence of only a trace amount of water, i.e., sufficient water to catalytically enhance the production of the tertiary amine borane complex but insufficient for forming two phases, e.g. the saturation level.
- the level of water will range from at least about 0.5% based on the weight of the solvent to the saturation point of water in the solvent. This may be from 1.2% for ethyl ether to 0.6% for isopropyl ether to 1.5% for tert-butyl ether to 3.3% for ethyl acetate.
- the tertiary polyamine or diamine results in a more water soluble product than does the monoamine borane and when present in a carboxylic acid containing aqueous medium the tertiaryamine borane is destroyed.
- Temperatures required for reaction of the tertiary amine with the alkali metal borohydride are conventional and typically range from about -25° to 30° C., preferably -15° to 15° C., with pressures ranging from atmospheric to 50 psig.
- MTEDA Methyl-triethylenediamine
- anhydrous Et 2 O was placed in a flask and the flask was purged with N 2 for ⁇ 15 minutes. To this was added 19 g NaBH 4 . The mixture was cooled to 0° C. with an ice bath and 63 g of crude MTEDA ( ⁇ 2.5% H 2 O content) was carefully added while observing the temperature. A solution of 30 g of glacial acetic acid in 30 mL anhydrous ethyl ether was prepared and placed in an addition funnel that was then placed on the flask. The amount of ether in the reaction flask was then adjusted so that it was approximately 250 mL.
- the acetic acid solution was slowly added, while stirring vigorously, over a period of 75 minutes at such a rate so as to maintain the reaction temperature at 3°-7° C. Vigorous gas evolution was noted. After the addition was complete, the temperature fell and the gas evolution slowed. Stirring was continued for 30 minutes and the temperature was slowly raised to room temperature. The flask was kept under a slow N 2 purge overnight. The next day, the solid residue was extracted with a total of 800 mL ether and 600 mL toluene. The extracts were dried to give a total of 62.5 g of waxy yellow solid (89% yield). This procedure gave yields of 69-92% (five runs) on this scale and 79-88% (four runs) when run at twice the scale. Yields were excellent.
- Example 1 The procedure of Example 1 was repeated except that the 1.5 ml H 2 O water addition was omitted. Glacial acetic acid was used as the protic acid source. A clear, colorless, liquid, as opposed to the white solid obtained in Example 1 was obtained. The liquid product was analyzed by 13 C NMR and analysis showed the liquid consisted of a 1:1 mixture of a methyl-triethylenediamine/BH 3 complex and an acetyl containing impurity.
- Methyl-triethylenediamine (63 grams) was charged to a vessel along with a suspension of 19.5 grams sodium borohydride in 300 mL's anhydrous acetonitrile. Carbon dioxide was bubbled through the suspension, while stirring, for about 90 minutes. The temperature was maintained at 20°-25° C. during the reaction period. A white product was obtained in about 87% yield.
- Example 3 in contrast to Example 3, showed that CO 2 was effective for effecting the reaction between methyl-triethylenediaine and sodium borohydride in an anhydrous medium while the protic acid, glacial acetic acid, was ineffective.
- the by-product acetyl containing impurity was not present when CO 2 was used as the reactant and it was concluded the reaction was by a different mechanism than that when protic acid was used.
- a mixture of 20 mL H 2 O and 500 mL hexane was placed in a flask and purged with a flow of N 2 .
- the flask was placed in an ice-bath and a solution of 40 g of NaBH 4 in 200 mL of H 2 O was added. Purging was continued and 127 g of MTEDA was added. Two phases were present. Carbon dioxide was bubbled through the mixture for ⁇ 6 hours with vigorous stirring. At the end of this time, the mixture was allowed to settle for ca. 1 hour.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention relates to a process for producing tertiarydiamine-boranes by reacting a tertiary diamine with a borohydride in the presence of a carboxylic or mineral acid source. Water is included in the reaction medium in a catalytic amount but insufficient for forming two phases. Excellent selectivity to tertiary diamine-boranes is achieved.
Description
This invention relates to a process for producing tertiary polyamine boranes by the reaction of a borohydride with a tertiary polyamine.
Tertiary amine boranes are utilized in many fields, which include the preparation of epoxy resins by acting as a curing agent or accelerators; in organic synthesis as reducing agent; as a reagent for the hydroboration of alkenes and in electroless plating applications. Essentially five methods have been developed for the synthesis of tertiary amine-boranes and these methods are described as follows:
1. The direct reaction of an amine and diborane;
2. Reacting tetrahydroborates with ammonium salts;
3. Transamination of aminoboranes;
4. The reaction of a metal tetrahydroborate with iodine in the presence of an amine; and
5. The reaction of a metal tetrahydroborate with carbon dioxide or carboxylic or mineral acid in the presence of an amine and organic solvent.
Many of the above methods were difficult to practice in the production of tertiary amine-boranes because of the required synthesis of various reactive materials, the handling of expensive or difficult to handle reagents and difficulty in product recovery.
Of the above synthesis techniques, the one which appears to be most widely utilized is synthesis route 5 which involves the reaction of a metal borohydride with a tertiary amine. The following patents are representative:
U.S. Pat. No. 3,013,016 discloses a process embraced within synthesis route 5 for producing trialkylamine boranes. A trialkylamine, e.g. trimethylamine or triethylamine, is contacted with potassium borohydride in the presence of an aqueous phase containing an inert organic solvent which is immiscible or only partially miscible with water. Carbon dioxide, or an acid source such as a carboxylic acid or mineral acid is added to the reaction medium. Reaction occurs at about 20°-40° C. and atmospheric pressure. The product is recovered by separating the organic solution containing the trialkylamine borane for the aqueous phase and then separating the organic solvent from the trialkylamine borane by distillation.
Czechoslovakian patent 242,064 discloses a process for producing tertiary amine-boranes via synthesis route 5 wherein an anhydrous suspension of a metal tetrahydroborate and tertiary amine in an organic solvent is contacted with carbon dioxide gas at temperatures ranging from about 0° to 50° C. for a period of 1-5 hours. The reaction product is washed with water, dried and the solvent evaporated.
British patent 909,390 discloses a process for producing amine boranes by reacting an amine salt with aqueous metal borohydride in organic solvent at room temperature under neutral or alkaline conditions. Product recovery is accomplished by separating the amine borane as it is formed by separating organic solvent containing the amine borane from the aqueous layer and then distilling the solvent from the amine borane.
Taylor, et al. in J. Am. Chem. Soc., vol. 77, 1955, pp. 1506-7 disclose the production of pyridine-borane complexes by reacting pyridine hydrochloride with sodium borohydride in the presence of pyridine solvent. Byproduct sodium chloride precipitates and unreacted pyridine hydrochloride is precipitated by the addition of ether. Unreacted pyridine is separated from the pyridine-borane reaction product by distillation.
This invention relates to an improved process for preparing amine boranes by the reaction of a metal borohydride with a tertiary amine in the presence of an inert, water immiscible organic solvent and a protic acid source. The improvement for enhancing yields in the production of the amine borane complexes having a water solubility greater than about 2 grams per 100 cc's at 25° C. and where the amine is a polyamine containing at least one tertiary nitrogen atom comprises effecting the reaction of the borohydride with the complex in the presence of water, wherein the water is present in a small but catalytically effective amount but insufficient for forming two phases. There are several advantages associated with the process of this invention. These advantages include:
an ability to produce tertiary amine-borane in high yield;
an ability to produce a commercially desirable white solid as product;
an ability to produce tertiary amine-boranes in a one-pot synthesis approach, and
an ability to separate the product from the reaction mixture with relative ease.
In the conventional preparation of tertiary amine boranes, a tertiary amine or salt is reacted with a borohydride under modest reaction conditions. In this case the tertiary amines are polyamines containing a tertiary nitrogen atom, e.g., diamines having from about 2-10 carbon atoms, which may be aliphatic or cyclic. Examples of tertiary amines include N-alkylated polyamines, e.g. methylated and ethylated derivatives of polyamines such as, ethylenediamine, propylenediamine, diethylenetriamine and triethylenetetraamine, e.g., methylated ethylenediamine or methylated propanediamine and methylated triethylenetetramine; cyclic amines, e.g. dimethylpiperazine, diethylpiperazine, triethylenediamine and methyltriethylenediamine; and ether amines, e.g., dimethylaminoethyl ether and bis morpholinoethyl ether. Of these polyamines, triethylenediamine and methyl-triethylenediamine are well suited for forming borane complexes.
The borohydrides which are reacted with the tertiary amine include alkali metal borohydrides such as sodium borohydride and potassium borohydride and lithium borohydride. Borane may also be used.
To facilitate reaction between the tertiary amine and borohydride, the reactants are dissolved in an organic solvent which is inert to the reaction medium. Conventional organic solvents, which are suited for producing tertiary amine boranes include hydrocarbons such as benzene, toluene, xylene; ethers such as diethylether, methodyethylether, dimethoxyethane, methyltert-butylether, dioxane, tetrahydrofuran and isopropyl ether; aliphatic hydrocarbons, i.e., those having from about 6 to 20 carbon atoms, e.g., hexane, pentane, dodecane, and the like. In addition various carboxylic esters such as ethylacetate, propylacetate and the like and nitriles such as acetonitrile can be used. The organic solvents used in the synthesis are well known and most will work so long as the reactant amine and product borane complex are soluble in the solvent and sufficiently volatile such that they can be distilled away from the reaction product.
The reaction of the tertiary amine with the alkali metal borohydride is carried out in the presence of a protic acid source, e.g. a C2-10, preferably a C2 -C4 carboxylic acid, or an anhydrous mineral acid. Examples of C2-10 carboyxlic acid sources include, acetic acid, propionic acid, butyric acid and examples of mineral acids include hydrochloric, phosphoric and sulfuric acids. When using a mineral acid it may be necessary to dilute such acids in an organic solvent as the anhydrous, concentrated mineral acids may be too strong and cause product decomposition.
In contrast to previous processes, the reaction is carried out in the presence of only a trace amount of water, i.e., sufficient water to catalytically enhance the production of the tertiary amine borane complex but insufficient for forming two phases, e.g. the saturation level. Typically, the level of water will range from at least about 0.5% based on the weight of the solvent to the saturation point of water in the solvent. This may be from 1.2% for ethyl ether to 0.6% for isopropyl ether to 1.5% for tert-butyl ether to 3.3% for ethyl acetate. In contrast to the prior art processes water is to be avoided in the reaction and in product recovery in order to maximize the yield of tertiary amine boranes produced and to facilitate the recovery of the tertiary amine borane from the reaction medium. When excess water is present in the reaction medium, as evidenced by two phases with the water immiscible organic solvent, yields typically drop because of movement of the tertiary amine borane from the organic solvent to the aqueous phase thus resulting in product loss. Although not intending to be bound by theory it is believed that the tertiary polyamine or diamine results in a more water soluble product than does the monoamine borane and when present in a carboxylic acid containing aqueous medium the tertiaryamine borane is destroyed.
Temperatures required for reaction of the tertiary amine with the alkali metal borohydride are conventional and typically range from about -25° to 30° C., preferably -15° to 15° C., with pressures ranging from atmospheric to 50 psig.
The following examples are provided to illustrate embodiments of the invention and are not an attempted to restrict the scope thereof.
Methyl-triethylenediamine (MTEDA) Borane In Presence of Water and an acetic acid suspension of 20 g NaBH4 in 375 mL anhydrous diethyl ether (specified as containing <0.01% water) was cooled to 2° C. in a cooling bath. To this was added 61.5 g of freshly distilled methyl-triethylenediamine (MTEDA, water content 600 ppm) and 1.5 mL H2 O. A solution of 30 g glacial acetic acid (99.7) in 30 mL anhydrous diethyl ether was added to the stirred suspension at such a rate that the addition was complete in 70 minutes and the reaction temperature did not exceed 5° C. The mixture was stirred an additional 40 min. at <5° C. and the cooling bath was then removed. Stirring was continued an additional 45 min. as the temperature rose to 18° C. The reaction mixture was then allowed to stand overnight. At this time, the mixture was filtered and the ether solution was removed to give 24.4 g of MTEDA/BH3 which was obtained as a white solid. The remaining solid from the filtration was washed thoroughly with toluene and the wash solution was taken to dryness to yield an additional 37 g of product. A product yield of about 87% was obtained.
Approximately 200 mL anhydrous Et2 O was placed in a flask and the flask was purged with N2 for ˜15 minutes. To this was added 19 g NaBH4. The mixture was cooled to 0° C. with an ice bath and 63 g of crude MTEDA (˜2.5% H2 O content) was carefully added while observing the temperature. A solution of 30 g of glacial acetic acid in 30 mL anhydrous ethyl ether was prepared and placed in an addition funnel that was then placed on the flask. The amount of ether in the reaction flask was then adjusted so that it was approximately 250 mL. The acetic acid solution was slowly added, while stirring vigorously, over a period of 75 minutes at such a rate so as to maintain the reaction temperature at 3°-7° C. Vigorous gas evolution was noted. After the addition was complete, the temperature fell and the gas evolution slowed. Stirring was continued for 30 minutes and the temperature was slowly raised to room temperature. The flask was kept under a slow N2 purge overnight. The next day, the solid residue was extracted with a total of 800 mL ether and 600 mL toluene. The extracts were dried to give a total of 62.5 g of waxy yellow solid (89% yield). This procedure gave yields of 69-92% (five runs) on this scale and 79-88% (four runs) when run at twice the scale. Yields were excellent.
This example shows that trace amounts of water can be added to the reaction medium by addition with the methyl-triethylenediamine feed in contrast to being added as a separate component as illustrated in Example 1.
The procedure of Example 1 was repeated except that the 1.5 ml H2 O water addition was omitted. Glacial acetic acid was used as the protic acid source. A clear, colorless, liquid, as opposed to the white solid obtained in Example 1 was obtained. The liquid product was analyzed by 13 C NMR and analysis showed the liquid consisted of a 1:1 mixture of a methyl-triethylenediamine/BH3 complex and an acetyl containing impurity.
Methyl-triethylenediamine (63 grams) was charged to a vessel along with a suspension of 19.5 grams sodium borohydride in 300 mL's anhydrous acetonitrile. Carbon dioxide was bubbled through the suspension, while stirring, for about 90 minutes. The temperature was maintained at 20°-25° C. during the reaction period. A white product was obtained in about 87% yield.
This example, in contrast to Example 3, showed that CO2 was effective for effecting the reaction between methyl-triethylenediaine and sodium borohydride in an anhydrous medium while the protic acid, glacial acetic acid, was ineffective. The by-product acetyl containing impurity was not present when CO2 was used as the reactant and it was concluded the reaction was by a different mechanism than that when protic acid was used.
A mixture of 20 mL H2 O and 500 mL hexane was placed in a flask and purged with a flow of N2. The flask was placed in an ice-bath and a solution of 40 g of NaBH4 in 200 mL of H2 O was added. Purging was continued and 127 g of MTEDA was added. Two phases were present. Carbon dioxide was bubbled through the mixture for ˜6 hours with vigorous stirring. At the end of this time, the mixture was allowed to settle for ca. 1 hour. Extraction of the aqueous slurry with 2×100 mL ethyl ether gave a yellow hexane/Et2 O solution which was evaporated to dryness to give about 5 g of a sticky yellow solid (ca. 5% yield).
This Example shows that reduced yields were obtained at the higher water level (compare Example 2). Apparently, the water interfered with the isolation.
In the conventional process of U.S. Pat. No. 3,013,016 conversion of trimethyl and triethylamine to a borane complex could be effected using CO2 in a two phase process. In contrast, the amine borane yield was quite low when a polyamine containing a tertiary nitrogen atom, i.e., methyl-triethylenediamine was used. Lower product yields are believed to be caused in part by inseparability of the product due to solubility of the product in the reaction mixture.
Claims (11)
1. In a process for producing amine boranes by the reaction of a metal borohydride with a tertiary amine in the presence of an inert organic solvent and a protic acid source, the improvement for enhancing formation of a borane complex of a polyamine containing a tertiary nitrogen atom as the tertiary amine which comprises:
effecting the reaction in the presence of water wherein the water is present in a catalytically effective amount but insufficient for forming two phases.
2. The process of claim 1 wherein the water is present in an amount of from 0.5% based upon the weight of the solvent to the saturation level.
3. The process of claim 2 wherein the acid source is a carboxylic acid wherein the carboxylic acid has from 2-10 carbon atoms.
4. The process of claim 3 wherein said polyamine containing a tertiary nitrogen atom is a cyclized diamine.
5. The process of claim 4 wherein said cyclized diamine is triethylenediamine or an alkyl derivative thereof.
6. The process of claim 5 wherein said cyclized diamine is methyltriethylenediamine.
7. The process of claim 3 wherein said polyamine is a methylated or ethylated derivative of diethylenetriamine or triethylenetetramine.
8. The process of claim 3 wherein said polyamine is methylated ethylenediamine or methylated propanediamine.
9. The process of claim 2 wherein said acid source is a mineral acid carried in an organic medium and said amine is triethylenediamine or methyltriethylenediamine.
10. A process for forming borane complex of triethylenediamine and methyl-triethylenediamine which comprises reacting methyl-triethyleneamine or triethylenediamine with sodium borohydride in the presence of C2-4 carboxylic acid and water wherein the water is provided at a level of from 0.5% by weight of the amine to the saturation level, the reaction being carried out at a temperature from about -25° to 30° C. and a pressure ranging from atmospheric to 50 psig.
11. The process of claim 10 wherein said carboxylic acid is acetic acid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US07/388,540 USH919H (en) | 1989-08-02 | 1989-08-02 | Process for producing polyamine boranes |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US07/388,540 USH919H (en) | 1989-08-02 | 1989-08-02 | Process for producing polyamine boranes |
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USH919H true USH919H (en) | 1991-05-07 |
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US07/388,540 Abandoned USH919H (en) | 1989-08-02 | 1989-08-02 | Process for producing polyamine boranes |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5144032A (en) * | 1988-10-05 | 1992-09-01 | E. I. Du Pont De Nemours And Company | Preparation of tertiary amine borane adducts |
EP0770617A1 (en) * | 1992-06-18 | 1997-05-02 | Boulder Scientific Company | Process for producing amine-boranes |
-
1989
- 1989-08-02 US US07/388,540 patent/USH919H/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
Taylor, M. D.,; Grant, L. R.; and Clifton A. Sands, "A Convenient Preparation of Pyridine-Borane" J. Am. Chem., vol. 77, 1955, pp. 1506-1507. |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5144032A (en) * | 1988-10-05 | 1992-09-01 | E. I. Du Pont De Nemours And Company | Preparation of tertiary amine borane adducts |
EP0770617A1 (en) * | 1992-06-18 | 1997-05-02 | Boulder Scientific Company | Process for producing amine-boranes |
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