US3379764A - Amination of alkylbromides - Google Patents

Amination of alkylbromides Download PDF

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US3379764A
US3379764A US484172A US48417265A US3379764A US 3379764 A US3379764 A US 3379764A US 484172 A US484172 A US 484172A US 48417265 A US48417265 A US 48417265A US 3379764 A US3379764 A US 3379764A
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reaction
alkylbromide
alkylbromides
temperature
dialkylamine
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US484172A
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Glen R Wyness
Douglas W Jensen
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to US484172A priority Critical patent/US3379764A/en
Priority to DE19661543820 priority patent/DE1543820C3/de
Priority to CH1259566A priority patent/CH475186A/de
Priority to NL6612303A priority patent/NL6612303A/xx
Priority to BE686237D priority patent/BE686237A/xx
Priority to GB38836/66A priority patent/GB1116614A/en
Priority to FR74845A priority patent/FR1491696A/fr
Priority to ES0330845A priority patent/ES330845A1/es
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/08—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings

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  • ABSTRACT OF THE DISCLOSURE Process for preparing trialkylamines from a mixture of alkylbromides containing alkyl groups of from to 20 carbon atoms, dialkylamines containing from 1 to 3 carbon atoms, and water, the molar ratio of dialkylamine to alkylbromides being in excess of about 8 :1 by reacting the alkylbromides with the dialkylamines for 2 to 7 minutes at a temperature of from 100 F. to 190 F. and thereafter heating the reaction product to a temperature of from 275 F. to 375 F. for from 4.5 to 12 minutes.
  • This invention relates to a process for the preparation of tertiary amines by aminating alkylbromides.
  • amine oxides as synthetic detergents has been the need in the detergent industry to find an improved method of preparing a relatively pure oxidizable tertiary amine product.
  • Such amines can be produced by aminating an alkylbromide.
  • alkylhalides An important source of alkylhalides is via a reaction between alpha olefin raw materials and, either, a halogen or a halide acid.
  • the a-olefins are converted to both primary alkylhalide, e.g., l-bromoalkane, and secondary alkylhalide or internal halide, e.g., 2-bromoalkane.
  • primary alkylhalide e.g., l-bromoalkane
  • 2-bromoalkane e.g., 2-bromoalkane.
  • a-Olefin raw materials also contain small amounts of branched chain olefins. These branched chain olefins are converted to branched chain alkylbromides by a free radical bromination reaction.
  • the reaction product will also contain small amounts, i.e., about 5% of internal bromides.
  • tertiary amines i.e., trialkyl amines
  • aminating alkylbromides comprising major portions of primary alkylbromides and minor portions of branched chain and secondary bromides, which process reduces or eliminates problems ordinarily connected with such amination.
  • Another object of this invention is to provide a process as described above which insures substantial completeness of the reaction.
  • a proces comprising the steps of (1) Preparing a reaction mixture containing an alkylbromide, said alkylbromide being comprised of a major portion of straight chain primary alkylbromides and a minor portion of straight chain secondary alkylbromides and branched chain primary alkylbromides, wherein the alkyl group of said alkylbromides contains from about 10 to about 20 carbon atoms; and a dialkylamine-water solution comprising a dialkylamine wherein the alkyl groups contain from 1 to about 3 carbon atoms; said dialkylamine-Water solution containing from about 5% to about 20% water by weight; the molar ratio of said dialkylamine to said alkylbromide in said reaction mixture being in excess of about 8: 1;
  • FIGURE 1 and FIGURE 2 are drawings showing time/temperature profiles characteristic of the amination reaction of the present invention.
  • reaction mixture comprising an alkylbromide, a dialkylamine and Water is prepared.
  • the alkylbromide raw material is comprised principally of a mixture of straight chain and branched chain primary and secondary alkylbromides.
  • the major portion of the alkylbromide raw material is straight chain primary alkylbromides making up from about to by weight of the alkylbromide raw material.
  • a minor portion of the alkylbromide raw material is a. mixture of from about 2% to about 5% by weight of straight chain secondary alkylbromide and from about 1% to about 4% of a branched chain primary alkylbromide.
  • FIGURES 1 and 2 illustrate that time/temperature profiles which characterize typical continuous and batch processes performed according to the present invention.
  • the drawings are deemed self-evident but it can be observed that each drawing shows two temperature levels, the first being considerably lower than the second.
  • the first relatively low curve represents the temperature prevailing during the first reaction step
  • the second elevated temperature curve represents the second reaction step.
  • there is a sharp inclined line indicating the end of a typical first reaction step and the initiation of a typical second reaction step.
  • the limits and ranges both in time and temperature are critical, and although they have been mentioned above, they are described in more detail below.
  • alkylbromides which comprise the alkylbromide raw material
  • the a-olefins as well as the parafiins are essentially inert throughout the process and do not interfere wit-h the reaction.
  • the alkyl group of the alkylbromide reactant of the initial reaction mixture can contain from about to about 20 carbon atoms. In a preferred embodiment of the invention, the alkyl group contains from 12. to 16 carbon atoms. These various chain length alkylbromides can be utilized individually per se or in combination with each other in any proportion.
  • Suitable primary straight chain alkylbromides are the following: l-bromodecane, l-bromoundecane, 1 bromododecane, 1 bromotridecane, l-brornotetradecane, l-bromopentadecane, l-bromohexadecane, l-bromoheptadecane, l-bromooctadecane, l-bromononadecane and l-bromoeicosane.
  • primary branched chain alkylbromides which accompany such primary bromides as used in this process are: l-bromo-Z-ethyldecane, 1-bromo-2-butyloctane, l-bromo- 2-ethyldodecane, l-bromo-Z-butyldecane, 1-bromo-2-hexyloctane, l-bromo-Z-ethyltetradecane, l-bromo-Z-butyldodecane and l-bromo-Z-hexyldecane.
  • Eaxrnplesof specific internal or secondary bromides which accompany such primary bromides as utilized in the process of this invention are 2-bromodecane, 2-bromoundecane, Z-bromododecane, 3 bromotridecane, 4 bromotetradecane, S-bromopentadecane, 2-bromohexadecane, 2-bromoheptadecane, 2-bromo-3-bromohexadecane.
  • the positioning of the bromine group can be on any of the carbons of the aliphatic chain.
  • the molecules can contain more than one atom of bromine.
  • the alkylbromide raw material employed in the amination process of this invention can be prepared, as mentioned above, by the reaction of hydrogen bromides with unsaturated hydrocarbons, e. g., alpha-olefins.
  • unsaturated hydrocarbons e. g., alpha-olefins.
  • the hydrogen and the bromine add across the carbon-carbon double bond; the hydrogen attaches itself to the carbon atom bearing the greater number of hydrogen atoms and the bromine attaches itself to the carbon atom bearing the least number of hydrogen atoms.
  • This mode of addition is termed the normal or Markownikoff addition, the product of which is a secondary bromide.
  • the alkylbromide utilized in this invention should, as described above, contain a primary bromide as a major ingredient, e.g., 90% to 95% by weight.
  • Primary bromides are formed by an addition process variously denoted as abnormal, anti-Markownikolf or free radical addition.
  • free radical addition can be effected.
  • free radical promoters such as peroxides, e.g., hydrogen peroxide or acetyl peroxide, as Well as compounds which tend to form peroxides when contacted with unsaturated compounds such as oxygen, air, or ozone can be utilized with hydrogen bromide and an ot-olefin to etfect free radical or anti-Markownikolf addition.
  • ultraviolet radiations can be used to promote or catalyze the abnormal addition of hydrogen bromide to unsaturated organic compounds.
  • alkylbromides for use in this invention which comprise a major portion of straight chain primary alkylbromides and a minor amount of straight chain secondary alkylbromides, and branch chain primary alklbromides.
  • Liquified dialkylamines utilized in this process have alkyl groups containing from 1 to about 3 carbon atoms.
  • the two alkyl groups of the amine molecule can consist of the same or different numbers of carbon atoms within the specified range.
  • the various amines, such as those listed below, can be used per se or in combination with each other in any amounts provided the essential molar proportions previously mentioned are adhered to.
  • dialkylamines suitable for use in this invention are the following: dimethylamine, diethylamine, dipropylamine, methylethylamine, methylpropylamine and ethylpropylamine.
  • the preferred dialkylamine for this process is dimethylamine.
  • a correspondingly higher pressure of above about 350 pounds per square inch should be utilized in this process to maintain dimethylamine in a liquified state.
  • the upper pressure limitation is governed only by the strength of the reaction vessel and the amount of pressure that can economically be applied. Pressures over 3000 pounds per square inch are, however, not commercially feasible and this can be regarded as the upper limit.
  • the preferred pressure throughout the reaction system is maintained in the range of from about 350 pounds per square inch gauge to about 1200 pounds per square inch gauge. These pressures must be maintained throughout the entire process to prevent volatilization of the dialkylamines.
  • Molar ratios of dialkylamine to alkylbromide greater than about 8:1 have been found to be satisfactory in this process. At any molar ratio in excess of about 8:1, the formation of quaternary ammonium compounds is effectively reduced and the reaction is substantially complete. The upper limitation on the molar excess is governed primarily by the size of the reactor and the desired output of the tertiary amine. However, in a preferred embodiment of this invention, a molar ratio of from 12:1 to 18:1 is utilized.
  • Water is added as an essential ingredient to the reaction mixture in critical proportions.
  • the addition of Water serves the useful purpose of increasing the reaction rate of the amination process.
  • an excess of water is added to the dialkylamine and alkylbromide, two phases, an oil phase and a water phase, will form.
  • Such a two-phase system substantially promotes the formation of the quaternary ammonium compounds and, thus, needs to be avoided.
  • from about 5% to about 20% water by weight of the dialkylamine-water solution is utilized in this invention. In no instance, however, should water be added to the reaction mixture in such amounts as to form two phases as hereinbefore described.
  • the water comprises from about 8% to about by weight of the dialkylamine-water solution.
  • water is introduced into the reaction mixture in the form of a dialkylamine-water solution.
  • the dialkylamines are soluble in water to a high degree, whereas the alkylbromides are not.
  • each of the essential reaction components i.e., alkylbromide, dialkylamine and water, can be brought together separately into a mixing pump. Provided that suflicient mixing is supplied and provided also that the dialkylamine and the alkylbromide are present in the requisite amounts, the reaction proceeds according to the contemplated method of the present invention.
  • the reaction mixture prepared according to the manner described above is then heated to initiate the reaction between the alkylbromide and the dialkylamine.
  • This is a highly exothermic reaction and the amount of heat applied to the reaction system should take the factor into consideration.
  • it is principally the straight chain primary alkylbromide ingredient which reacts with the dialkylamine to form the desired tertiary amine. This is so because the temperature is held to a level in the range of from about 100 F. to about 190 F., and in this temperature the rate of reaction of the straight primary alkylbromide is considerably faster than either of the aforementioned minor alkylbromide components.
  • this first reaction stage takes from about 2 to about 7 minutes.
  • the reaction is conducted at a temperature in the range of from 120 F. to about 170 F. for a period of from about 3 to about 5 minutes, not counting the time required to heat to that temperature range.
  • the reaction between the alkylbromide and the dialkylamine is highly exothermic. It may be necessary, therefore, to provide the reaction system with a heat exchanger to aid in maintaining the reaction temperature in the broad range of 100 F. to 190 F. and preferably in the preferred range of 120 F. to about 170 F.
  • This completion percentage corresponds to the amount of straight chain primary alkylbromide present as the major component.
  • one of the critical requirements of the present reaction system is maintaining a suflicient pressure within the system to keep the dialkylamine reactant as a liquid.
  • these pressures can vary from a minimum of about 75 pounds per square inch gauge up to any commercially feasible maximum.
  • Preferred pressure limitations with the preferred dialkylamine, i.e., dimethylamine are from about 350 pounds per square inch gauge to about 1,200 pounds per square inch gauge.
  • the reaction product thereof comprises a major proportion of trialkylamines due to the virtually complete conversion of the straight chain primary alkylbromide to the desired tertiary amine.
  • the remainder of the reaction product is principally the as yet unreacted straight chain secondary alkylbromides, the branched chain primary 'alkylbromides, dialkylamine, and water.
  • the reaction product from the initial low temperature reaction is quickly heated to a temperature of from about 275 F. to about 375 F. and held there for -a period of from about 4.5 to about 12 minutes.
  • the temperature for this high temperature phase of the reaction should be from about 300 F.
  • the final reaction product contains only negligible amounts of the undesired quaternary ammonium compounds.
  • the amount of regenerated olefin is held to an absolute minimum.
  • the interval between the completion of the first low temperature reaction and the initiation of the high temperature reaction stage should, as a practical matter, be as short as possible. No advantage is gained by interrupting the reaction at this point. In a continuous process, for instance, there need be no delay between these steps, the reaction product passing directly from one stage to the second stage.
  • the high temperature needed for the second stage can be supplied by any means such as a heat exchanger 'or a heating water or steam jacket.
  • a heat exchanger is a preferred embodiment, and in a batch reaction system, the reactor vessel can be surrounded with a hot water or steam jacket.
  • the reaction product is comprised predominantly of a desired tertiary amine, e.g., on the order of about 98 %-99%.
  • This reaction product can be directly oxidized to yield an excellent highly effective amine oxide detergent composition.
  • the reaction product of the high temperature reaction step is comprised of the following reaction products.
  • the major ingredient is the desired tertiary amine. Since the dialkylamine reactant is added in the large molar excess described earlier, there is still unreacted dialkylamine remaining.
  • Hydrogen bromide is formed as a by product during the reaction between the alkylbromide and the dialkylamine. The hydrogen bromide forms a salt with the available excess dialkylamine and is present in that form. Besides these reaction products there can be present in varying but always minor amounts of unreacted alkylbromide, regenerated olefin, and vinylidene branched olefins.
  • Separation of the desired tertiary amine reaction product can be performed in any devised manner. While not an essential step of the present invention, recovery of the tertiary amine is usually performed by adding a slight excess of sodium hydroxide to the final reaction prodnot. This results in the formation of a brine solution which is then passed to a distillation column where the diallaylamine is stripped 01f. One convenient way of doing this is by passing steam through the brine solution. The stripped off dialkyla'mine can be recycled back to the first step of the reaction.
  • the remaining reaction product is allowed to stand under pressure for a period of time.
  • Two phases gradually appear; the lower phase is essentially trialkyl amines and the upper phase is essentially sodium bromide and water. These phases are easily separated and the sodium bromide is recovered and the water is discarded.
  • the phase containing the tertiary amines is distilled. The distillate is the water-white trialkyl amine.
  • the process of this invention can be accomplished in both batch and continuous processes. In both cases, however, the particular reaction vessel utilized must be capable of withstanding relatively high pressures and must be capable of effecting a two-step temperature reaction as related above. Furthermore, the batch reaction vessel must be equipped with an agitating device to eifect the good mixing which, as mentioned above, is desirable. Suitable reaction vessels for the process of this invention are generally described in Perrys Chemical Engineers Handbook (3rd edition, 1950), at pages l2561258.
  • the reaction vessel utilized in this example of the above related process was a tubular reactor.
  • the major component of the reactor was a schedule 80 stainless steel pipe of three-quarter inch nominal inside diameter which was 500 feet long.
  • One heat exchanger was provided which permitted gradual heating of the reaction components in the first 100 feet of the reactor.
  • Another heat exchanger was located at 200 feet from the reactor inlet. This heat exchanger permitted rapid heating of the reaction components and products.
  • the entire system was insulated to prevent major heat losses.
  • the alkylbromide was comprised by weight of 88.8% primary straight chain alkylbromides, i.e., 57.6% l-bromododecane, 22.3% 1brom0tetradecane and 8.9 l-bromohexadecane, 3.5% branched chain primary alkylbromides, 5% straight chain secondary alkylbromides, 1.7% paraffins and 1.0 a-olefins.
  • the chain length of the alkyl groups in the alkyl bromide reactant was a mixture of 12, 14 and 16 carbon atoms.
  • This mixture was introduced into the above-described tubular reactor and heated until the temperature rose to 178 F.
  • the reaction mixture was in a temperature range of 100 F. to 178 F. for about 2.7 minutes. It was maintained at 178 F. for 1.6 minutes. At this point, the temperature of the mixture was abruptly raised to 303 F.
  • the yield of desired tertiary amine alkyldimethylamine was over based upon the alkylbromide feed stream.
  • the yield of dialkyldimethyl quaternary ammonium bromide impurity was only 0.17% by weight of the total reaction product.
  • Water was continuously metered into a dimethylamine stream so as to form a dimethylamine-water solution containing 13% by Weight of water.
  • the dimethylaminewater mixture was then metered into an alkylbromide stream at a molar ratio of dimethylamine to alkylbromide of 13:1.
  • the alkylbromide had the same chain length distribution as in Example I above and was comprised by weight of 88.8% primary straight chain alkylbromides, i.e., 57.6% l-bromododecane, 22.3% l-bromotetradecane and 8.9% l-bromohexadecane, 3.5% branched chain primary alkylbromides, 5% straight chain secondary alkylbromides, 1.7% paraffins and 1.0% a-olefins.
  • This mixture was introduced into the above-described tubular reactor. During the first 3.2 minutes the temperature was gradually raised from 80 F. to 178 F. The temperature was in a range of F. to 178 F. for about 2.7 minutes. At this point, the temperature was abruptly raised to 326 F. and held there for 4.8 minutes, after which the temperature was reduced to room temperature.
  • dialkyldimethyl quaternary ammonium bromide impurity was only 0.13% by weight of the total reaction product.
  • the yield of the desired alkyldiniethylamine product was over 95.5 based upon the alkylbromide feed stream.
  • alkylbromide In all of the following runs, a mixture of alkylbromide, dimethylamine and water was prepared.
  • the alkylbromide in all runs was comprised by weight of 93.2% primary straight chain alkylbromides, i.e. 57.2% 1- bromododecane, 22.3% l-bromotetradecane and 8.9% 1- bromohexadecane, 3.5% primary branched chain alkylbromides, 5% secondary alkylbromides, 1.7% parafiins and 1.0% a-olefins.
  • This mixture was introduced into the abovedescribed tubular reactor. During the first 3.2 minutes, the temperature was gradually raised from 80 F. to 178 F. At this point, the temperature was abruptly raised to 326 F. and held there for 4.8 minutes, after which the temperature was reduced to room temperature.
  • dialkyldimethyl quaternary ammonium bromide The yield of dialkyldimethyl quaternary ammonium bromide was only 0.13% by weight of the total reaction product. The yield of alkyldimethylamine was over 95.5% based upon the alkylbromide feed stream.
  • alkylbromide the alkyl group being a mixture of C to C carbon atoms, predominantly C to C dimethylamine and water was prepared.
  • the alkylbromide in all runs was comprised by weight of 93.2% straight chain primary alkylbromides, 2.5% branched chain primary alkylbromides, 3% secondary alkylbromides, 1.2% parafiins and 0.1% a-olefins.
  • the procedure followed in Example I was followed herein. The results of four runs are tabulated below.
  • Temperatures in (3) in the above table are part Of initial reaction of the heretofore discussed process. Temperature Shown in (5) above are representative of the second stage of the process.
  • the reaction vessel utilized in this example was a 1- gallon batch reaction vessel capable of withstanding a pressure up to 1,000 pounds per square inch gauge. This reaction vessel was fitted with a stirring device and thermometer.
  • the dimethylamine-water solution containing the percentages of water shown in Table 2 were placed in the reactor and heated to the temperature specified in the table below.
  • Alkylbromide (the alkyl group being a mixtur of C to C carbon atoms, predominantly C to C comprised by weight of 93.2% primary straight chain alkylbromide, 2.5% primary branched chain alkylbromides, 3% secondary alkylbromide, 1.2% paraflins and 0.1% a-olefins, was heated outside the reactor and injected into the batch reactor in the hereinafter stated mol ratio of dimethylamine to alkylbromide. The reaction was allowed to proceed under nearly adiabatic conditions under which the temperature of the reaction stabilized. The temperature was then increased to 300 F. for 9 minutes.
  • alkylbromides and dialkylamines e.g., diethylamine
  • the amounts of each component can be varied within the ranges delineated in the foregoing discussion.
  • the residence time in the reactor and the temperature of the reaction can be varied within the limits discussed previously.
  • a process for preparing trialkylamines comprising the steps of (l) preparing a reaction mixture containing an alkylbromide, said alkylbromide comprised of a major proportion of straight chain primary alkylbromides and a minor portion of straight chain secondary and branched-chain primary alkylbromides wherein the alkyl group of said alkylbromides contains from about 10 to about 20 carbon atoms; and a dialkylamine-water solution comprising a dialkylamine wherein the alkyl groups contain from 1 to about 3 crabon atoms; said dialkylamine-water solution containing from about 5% to about 20% water by weight; the molar ratio of said dialkylamine to said alkylbromide in said reaction mixture being in excess of about 8:1;
  • reaction product thereafter heating said reaction product to a reaction temperature of from about 275 F. to about 375 F. for from about 4.5 to about 12 minutes and under sufiicient pressure to maintain the dialkylamine in a liquified state.
  • dialkylaminewater solution contains from about 8% to about 15% water by weight.
  • step 2 is from about 3 to about 5 minutes at a temperature of from about F. to about F. and the residence time in step 3 is from about 5 to about 9 minutes at a temperature of from about 300 F. to about 350 F.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US484172A 1965-09-01 1965-09-01 Amination of alkylbromides Expired - Lifetime US3379764A (en)

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Application Number Priority Date Filing Date Title
US484172A US3379764A (en) 1965-09-01 1965-09-01 Amination of alkylbromides
DE19661543820 DE1543820C3 (de) 1965-09-01 1966-08-16 Verfahren zur Herstellung von Trialkylaminen
NL6612303A NL6612303A (xx) 1965-09-01 1966-08-31
BE686237D BE686237A (xx) 1965-09-01 1966-08-31
CH1259566A CH475186A (de) 1965-09-01 1966-08-31 Verfahren zur Herstellung von Trialkylaminen
GB38836/66A GB1116614A (en) 1965-09-01 1966-08-31 Amination of alkylbromides
FR74845A FR1491696A (fr) 1965-09-01 1966-08-31 Amination de bromures d'alkyle
ES0330845A ES330845A1 (es) 1965-09-01 1966-09-01 Procedimiento para la preparacion de trialquilaminas.

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US484172A US3379764A (en) 1965-09-01 1965-09-01 Amination of alkylbromides

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US (1) US3379764A (xx)
BE (1) BE686237A (xx)
CH (1) CH475186A (xx)
ES (1) ES330845A1 (xx)
GB (1) GB1116614A (xx)
NL (1) NL6612303A (xx)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3742060A (en) * 1969-11-24 1973-06-26 Gulf Research Development Co Preparation of amines
JPS5259162A (en) * 1975-11-07 1977-05-16 Searle & Co Preparation method of tertiary amine
US20060106255A1 (en) * 2004-11-15 2006-05-18 Kenneally Corey J Process of making long chain internal fatty tertiary amines

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3742060A (en) * 1969-11-24 1973-06-26 Gulf Research Development Co Preparation of amines
JPS5259162A (en) * 1975-11-07 1977-05-16 Searle & Co Preparation method of tertiary amine
DE2650961A1 (de) * 1975-11-07 1977-05-18 Searle & Co Verfahren zur herstellung von tertiaeren aminen
US4086234A (en) * 1975-11-07 1978-04-25 G. D. Searle & Co. Process for the preparation of tertiary amines
JPS6224428B2 (xx) * 1975-11-07 1987-05-28 Searle & Co
US20060106255A1 (en) * 2004-11-15 2006-05-18 Kenneally Corey J Process of making long chain internal fatty tertiary amines
US7342136B2 (en) * 2004-11-15 2008-03-11 Procter & Gamble Company Process of making long chain internal fatty tertiary amines

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NL6612303A (xx) 1967-03-02
DE1543820A1 (de) 1970-02-05
BE686237A (xx) 1967-02-28
ES330845A1 (es) 1967-07-01
GB1116614A (en) 1968-06-06
CH475186A (de) 1969-07-15
DE1543820B2 (de) 1976-01-22

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