BE617842A - - Google Patents

Description

       

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  * Improvements in conversion reactions of organic compounds and catalysts used "
The present invention relates to reactions for the conversion of organic compounds and to solvent systems making it possible to facilitate these reactions. The present invention relates in particular to the use of a base-solvent or alkali metal-solvent system, or the carrying out of a series of chemical conversion reactions which proceed by the mechanism of the carbanion.

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   Reactions using the carbanion mechanism are well known in the art and have been used in a variety of chemical conversions. These reactions develop through the formation of a carbanion intermediate, that is to say a negatively charged carbon ion. Strong basic catalysts, such as Group I metals, especially alkali metals, such as sodium and potassium, are commonly used (See U.S. Patent 2,952,719).



  In order to facilitate these reactions, solvents of the ether type, such as tetrahydrofuran, have been used. The use of solvents to enhance the reactivity of reactions is well known (see, eg, Lohse, Catalytic Chemistry, Chemical Publishing Company, Inc., New York, 1945, pages 75-76).



   Despite advances in solvent and catalyst technology, many reactions have not reached a commercially acceptable stage because of the stringent conditions required to stabilize the carbanion. With some reagents, stabilization of the carbons has been impossible for all practical purposes.



   According to the present invention, it has been found that by using particular solvent-base or solvent-alkali metal systems, it is possible to carry out a series of chemical reactions which develop by the mechanism of the carbanion, reactions which were heretofore. now of such a low reaction rate as to be industrially unacceptable. In particular, it has been found that carbanion reactions involving weakly ionizable C-H bonds can be carried out.



   The particular solvent employed is of critical importance. These solvents can be defined as having the following characteristics: (1) they are aprotic, i.e.

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 say that they should neither give nor easily accept a proton; (2) a high dielectric constant, exceeding 15 to 25 C; (3) they are dipolar; (4) they are non-hydroxylic.



    Obviously, the solvents employed in the present invention should be resistant to decomposition in the presence of the base or alkali metal employed and the reactants.



   Among the solvents of interest are the organic compounds having the following dipolar groups: carbonyl, a divalent CO radical; (2) phosphoryl, a trivalent PO radical; (3) sulfinyl or tallow oxide, the divalent SO radical; (4) sulfonyl or sulfone, the divalent SO2 radical; (5) and thiocarbonyl, the divalent CS radical. Examples of such solvents are dipolar compounds, such as alkyl tallow oxides, such as dimethyl tallow oxide and diisopropyl tallow oxide; thiophenes, such as tetrahydrothiophene-1,1-dioxides; alkyl formamides, such as N, N-dimethyl formamide; alkyl phosphoramides, such as trimethyl phosphoramide; and thioureas such as N, N'-dimethyl thiourea.



   A preferred group of solvents, especially in the case of carrying out oxidation reactions, or for use in conjunction with alkali metals, in addition to the properties defined above, also exhibit the following characteristics; the dipole group is free of hydrogen, and (2) adjacent atoms of the dipole group are free of hydrogen. Examples of the carbonyl compounds are tetraalkyl substituted ureas, such as tetramethyl urea, and substituted amides, such as t-butyl N, N-dimethyl formamide. Compounds having the phosphoryl radical are hexa-substituted phosphoramides, such as hexamethyl phosphoramide, tri (ethylene amide) phosphoramide, and hypophosphite ethers.

   The compounds

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 containing sulfinyl are sulfonamides substituted by tetraalkyl, such as tetramethyl sulfonamide and bis-dialkyl amino tallow oxide. An example of the sulfones is tetramethyl sulfone, and an example of the compounds having a thiocarbonyl group is formed by the alkyl substituted thioureas, such as tetramethyl thiourea.



   The most particularly preferred solvents for dissolving alkali metals are compounds having a phosphoryl radical. These compounds can be defined generically by the formula:
 EMI4.1
 wherein Y is oxygen, nitrogen or sulfur; R is an alkyl or aryl radical, and n is the valence of Y.



  Many compounds meeting this generic definition are well known.



   When Y is respectively formed by nitrogen, oxygen and sulfur, the classes of compounds can be described as being phosphoramides, normal phosphates and oxides of trithiophosphene, respectively. Hexa-substituted phosphoramides, such as hexamethyl phosphoramid [(CH3) 2N] 3P = O, are examples of phosphoramides.



  In addition, trimethyl phosphate (CH30) 3P = 0 is an example of normal phosphates and tris (methyl mercapto) phosphate (CH3S) 3P = O oxide is an example of trithiophosphene oxides. It is preferred that Y is hydrogen, i.e. that one has phosphoramides. As to R, it is preferable that it is selected from an alkyl or aryl group, so that the resulting compound is a liquid. For example, when R is an alkyl group, one prefer that it has 1 to 6 carbon atoms per radical.

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   The alkali metal employed in the present invention can be any of the monovalent elements of the first group of the periodic system. This group includes lithium, sodium, potassium, rubidium and cesium. The activity of the metals, when added to the above solvents, has been found to be inversely proportional to atomic weight, ie the lighter metals are the most active.



   The solubility of the alkali metals in 100 cc of hexamethyl phosphoramide at room temperature is given in the following table:
Table I
 EMI5.1
 
The amount of alkali metal which is dissolved in the solvent of the present invention can vary over a wide range. Generally, it is preferable to use a saturated solution at room temperature; however, this is primarily a practical consideration, as even a trace of alkali metal will serve to catalyze many reactions. Reactions which require the presence of oxygen or another material which is detrimental to the alkali metal or the solvent should be avoided. the base employed can be any of a wide variety of materials.

   The only limitation with respect to this material is that it must have sufficient basicity to allow the reaction to proceed. Examples of suitable bases are metal hydrides, such as sodium hydrides; inorganic amides of metals, such as sodium amide, organic amides of alkali and alkaline earth metals, such as methyl sodium amide

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 dium; metal alcoholates, such as sodium methoxide and potassium tertiary butoxide; metal hydroxides, such as caustic soda and cesium hydroxide; and the wings of metals such as sodium ethyl or lithium butyl. Especially preferred are bases composed of the heavy alkali metals, for example potassium, cesum and rubidium.

   Further, when the base has an alkyl group, the efficiency is increased by increasing the number of carbon atoms. For example, KOC2H5 is more efficient than KOCH3 and tertiary butoxide from KO is more efficient than the previous two.



   The particular conversion reactions referred to encompass a wide variety of known reactions. Generally speaking, almost any organic compound having an acidic hydrogen atom attached to a carbon atom can be reacted which can be removed to form the carbanion intermediate.

   The following list gives the main reactions: (1) polymerization of olefins, diolefins and vinyl-type compounds; (2) aldol and Cannizzaro condensations, the condensation of malonic esters and Michael type additions; (3) alkylations of aromatic side chains with olefins, ketones with organic halides and metal alkyls with olefins; (4) isomerization of the olefinic double bond and that of the backbone; (5) a. carboxylation of alkyl aromatics, such as toluene to produce phenylacetic acid; b. carboxylation of olefins, such as propylene, to give acrylic acid;

   (6) carbonylation of alkyl aromatics, olefins, etc. with carbon monoxide to give aldehydes;

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 (7) generation of carbene from halogen substituted compounds, ethers, sulfides, ammoniacal salts, etc. and the addition of the carbenes formed to olefins, diolefins and aromatics; (8) homogeneous hydrogenation of olefins, diolefins and aromatics; (9) hydroboration of olefins and diolefins; (10) formation of vinyl ethers by reaction of alkyls and alcohols; (11) benzene forming reactions, using any of the known benzene precursors and any of the known reactions.



  (12) formation of silene and reactions thereof; (13) a. oxidation of alkyl aromatics, such as toluene, xylene, mesitylene etc., to give mono and dicarboxylic acids; b. oxidation of various alkylated, arotated and sulfurized aromatic compounds, in particular alpha, beta and gamma picolines, and various alkyl thiophenes to the corresponding mono and diacids; vs. oxidation of olefins to acids; d. oxidation of all the materials included in a, b, and c including ammonia as a base, so that the ammoniacal salt is produced directly; e. direct oxidation of benzene to phenol; f. oxidation of the compounds mentioned under a, b and c to alcohols; g. oxidation of alkyl aromatics to ketones, for example oxidation of ethyl benzene to acetophenone;

   h. oxidation of mercaptans to disulfides or sulfonic acids; (14) production and reaction of organo-metallic products, such as:

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 at. Grignard reagents from organic halides and magnesium; b. metal alkyls from metals and organic halides.



   Since these systems facilitate ionic reactions, reactions involving organometallic compounds will be improved. An example of a reaction of organometallic compounds is that of benzyl halides with an alkali metal to form alkali metal benzyls. These latter compounds can then be reacted with a variety of compounds, such as ketones and aldehydes. In particular, when benzyl chloride is reacted with sodium, sodium benzyl is formed. The latter compound can be prepared to react with acetone to form dimethyl benzyl carbinol. It should be noted that in these reactions dissolved sodium (from the solvent-alkali metal system) is one of the constituents consumed by the reaction.



   The reaction phase can be homogeneous or heterogeneous depending on the particular system and the particular reaction.



  When the base is soluble in the following, for example the various alcoholates (potassium tertiary butoxide), the reaction is then homogeneous in base and, if desired, can be homogeneous in hydrocarbon; for example, olefins are soluble to a level of about 10 volumes per 1 at 25 ° C in hyexamethyl phosphoramide. In practice, the isomerization reaction could be carried out heterogeneously when the olefins are separated by a simple mixing and deposition operation. Some bases, such as caustic potash and caustic soda, are insoluble, and in this case a fixed bed could be employed with the hydrocarbon and solvent in contact with the solid base.

   These considerations

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 hold true for reactions involving hydrocarbons alone, for example isomerization, polymerization and aldolization.



   Obviously, when a gas is present, such as oxygen, carbon monoxide or carbon dioxide, the foregoing considerations will remain correct, but the reaction zone will also contain another gas phase.



   The particular ratios of solvent to base and base to reagent depend on a number of factors. For example, in homogeneous systems, it is desirable to have at least 10% by weight of base dissolved in the solvent until saturation. It is preferred that 20 to 40% by weight of the solvent-base system is constituted by a base. In heterogeneous base-solvent systems, the base is virtually insoluble. However, the amount of solvent present must be sufficient to ensure wetting of the surface of the base.



  A larger amount of solvent can be employed if it is desirable to dissolve the feed. In the case of the polymerization of olefins, small amounts of base may be employed, the amount thereof being determined by the particular molecular weight desired for the polymer produced.



  The fact that lower concentrations of base give higher molecular weight polymers and well known in the art, as does the amount of base which should be employed for a particular molecular weight range).



   The ratio of the amount of base to reactants also depends on a number of factors, such as the particular base-solvent system and the reaction contemplated. However, this ratio should be adjusted so as to allow the reaction to develop at a rate of at least 0.1 weight of feed per hour per weight of catalyst. This choice of variables can easily be determined by a specialist in

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 matter.



   In carrying out the reactions reported herein, temperatures of 15 to 400 ° C., preferably 20 to 150 ° C. As would be expected, higher temperatures accelerate the reaction; however, too high temperatures can be detrimental to the solvent-base system and to the selectivity of the reactions.



   In oxidation reactions, it is desirable to control the temperature very precisely. Temperatures above 200 C should preferably be avoided. Oxidation temperatures should preferably be maintained between 20 and 80 C.



   When using an alkali metal-hexamethyl phosphoramide catalyst composition, an upper limit of about 30,000 is desirable, since above this temperature the system may decompose. Likewise, the lower limit is set by the freezing point of the solvent and reagents.



   Another advantage of the present solvent-based systems is that, in isomerization, high stereo-selectivity to the isomer is obtained. This is especially true when a small alkyl group is attached to the length carbon atom of the neighbor of the double bond. As the alkyl group increases, the selectivity decreases. For example, a tertiary butyl group reduces the stereoselectivity of the isomerization reaction by 20 fold compared to a methyl group.



   Although the expressions "solvent system", "solvent", "dissolve" and "saturated solution" have been used in the present description, it will be understood that the exact physical and chemical phenomenon which takes place during the addition of the alkali metal solvent may not fully agree

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 with common use of this terminology.



   Although the fundamental nature of alkali metal phosphoramide solutions is not known experimentally, the following considerations are obvious. The phosphorus in the P = O bond can accept an electron in its d-orbitol.



  Thus, with readily ionizable materials, such as alkali metals, there may be a situation where the alkali metal ionizes and the electron is "solvated" by the solvent. Preliminary electron spin resonance studies show that this can happen. The metal cation can in turn be solvated by bonding to the oxygen function.



   Exampleē1
This example relates to the isomerization of 2-methyl-pentene-1 using the base-solvent system of the present invention. In carrying out this, the base is first dissolved in the solvent so as to produce a concentration given in the following table. The olefin is then introduced into the base-solvent system and stirred mechanically. The percentage by weight shown in the table for the 2-methylpentene-2 formed is the amount of conversion after 24 hours. All of the potassium tertiary butoxide and sodium amide are dissolved in the solution.



  On the other hand, all of the caustic potash was not dissolved.

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    TABLE I ISOMARIZATION OF 2-METHYLPENTENE-1
 EMI12.1
 
<tb> Temp. <SEP> - <SEP> 55 C. <SEP> Solvent <SEP> - <SEP> Dimethyl <SEP> <SEP> Sulfoxide
<tb> Base <SEP> Concentration <SEP> Ratio <SEP> Olefin <SEP> ¯ <SEP>% <SEP> in <SEP> weight
<tb> Base <SEP> Concentration <SEP> Ratio <SEP> Base-Solvent <SEP> of <SEP> 2-methylpentene-2 <SEP> *
<tb> KOH1 <SEP> 30 <SEP> g <SEP> 150 <SEP> ce. <SEP> 12.3
<tb> 150 <SEP> ce. <SEP>
<tb> tertiary <SEP> <SEP> <SEP> K <SEP> 0.65 <SEP> N <SEP> 200 <SEP> cc. <SEP> 22.6
<tb> 100 <SEP> cc.
<tb>



  NaNH2 <SEP> 3.2 <SEP> N <SEP> 150 <SEP> ce. <SEP> 20.3
<tb> 150 <SEP> ce. <SEP>
<tb>
 



    #% conversion in 24 hours, the initial 70 by weight of 2-methylpentene-2 being zero.



  1. The 'KOH did not completely dissolve.

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   As will be appreciated, yields greater than 20% by weight of 2-methylpentene-2 were obtained at the end of the 24 hour period, the efficiency of the conversion being proportional to the strength of the conversion. base used.



   Example 2
In a manner similar to that described in Example 1, 2-methylpentene-1 was contacted with various base-solvent systems. Table II gives the proportion of the reagent and of the solvent-base system and the degree of conversion of olefin obtained.

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    TABLE II ISOMERIZATION 55 C. Atmospheric pressure
 EMI14.1
 
<tb> Olefin, <SEP> cm3
<tb> 2-methylpentene-l <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 20 <SEP> 20
<tb> Solvent, <SEP> cm <SEP> 3 <SEP> (25 C.)
<tb> Sulfoxide <SEP> of <SEP> Dimethyl <SEP> (44) <SEP> 100 <SEP> 100 <SEP> 100
<tb> Tetrahydrofuran <SEP> (3) <SEP> 200
<tb> T-butyl alcohol <SEP> <SEP> (8)
<tb> Base <SEP> (moles <SEP> in <SEP> the <SEP> solvent)
<tb> Butylate <SEP> tertiary <SEP> of <SEP> Na <SEP> 0.4
<tb> Tertiary <SEP> <SEP> <SEP> K <SEP> 0.4 <SEP> 1.0 <SEP> 1.0
<tb> Butylate <SEP> tertiary <SEP> of <SEP> Os <SEP> 0.4 <SEP> '
<tb> <SEP> rate of <SEP> conversion <SEP> of olefin
<tb> (Kminutes-1) <SEP> 5x10-2 <SEP> 0.5x10-2 <SEP> 1,

  7x10-5 <SEP> 0 <SEP> 0
<tb>
 

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 The previous results clearly show the superiority of the solvents defined by the present invention, i.e. dimethyl sulfoxide over tetrahydrofuran and tertiary butyl alcohol, i.e. solvents which were commonly used in the prior art. Virtually no conversion was obtained with these common solvents. It should be further noted that the olefin conversion rate is closely proportional to the alkali metal forming the base. The conversion rate increases markedly with increasing molecular weight of the alkali metal.

   For example, the conversion rate with tertiary cesium butoxide is ten times more reactive than that obtained with tertiary potassium butoxide and almost three hundred times higher than that obtained with sodium tertiary butoxide.



   Example 3
To demonstrate the stereoselectivity of the solvent-base systems of the present invention, 20 cc of butene-1 was isomerized in 200 cc of dimethyl sulfoxide and 1 mole of potassium tertiary butoxide. 80% conversion of butene-2, 76 to cis-2-butene and 4% to trans-2-butene was obtained.



   Example 4
To show that a wide variety of olefins can be isomerized according to the present invention, 20 cc of various olefins were isomerized at 55 C. The system used was formed by 1 mole of potassium tertiary butoxide dissolved in 200 cc of dimethyl sulfoxide. . In all cases, yields of 100% of the isomerized product were obtained without side reactions. The reaction rate and the products formed are given in the following table.

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  TABLE III
 EMI16.1
 Reaction rate, Olefin Product constant, K tln-1 ¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ x 103 * = c # c CC = C ois & t JL 12,000 C = CCC cis & t CC = CC 120 C = CCCC cis & t CC = CCC 50 C = CCCCC cis & t CC = CCCC 48 cis & t CCC = CCC CC t C = CCCC CC = CCC 33 CCC = CCCC cis & t CC = CCC 3 CCCC "1 C = CCCC CC = CCC 0.1 CC
Example 5
0.1mole of n-butyl mercaptan was oxidized in 100 cc of methanol, tetrahydrofuran, dioxane, diglyme, N, N-dimethylormamide, and dimethyl acetamide at 23.5 # 0.2 C respectively under constant pressure of oxygen from an atmosphere. 0.2 moles of sodium methoxide was used in each treatment, resulting in a 2/1 molar ratio of base to mercaptan.

   Each oxidation was achieved to about 40-50%. The amount of mercaptan converted to bisulfide at any given time was determined by the amount of oxygen consumed, as it was experimentally determined that the stoichiometry for disulfide formation assumes a 4/1 molar ratio of mercaptan to. oxygen.



   The constants for the oxidation of n-butyl mercaptan to disulfide in each solvent, as well as the rates relative to the oxidation in methanol, are given in Table IV below.

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   TABLE IV Oxidation of n-butyl mercaptan in non-hydroxylated solvents
 EMI17.1
 
<tb> Solvent <SEP> K <SEP> x <SEP> 103, <SEP> Min.-1 <SEP> K <SEP> by <SEP> ratio <SEP> to
<tb>
<tb>
<tb>
<tb> methanol
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Methanol <SEP> 3.22 <SEP> 1
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Tetrahydrofuran <SEP> 116 <SEP> 36
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Dioxane <SEP> 989 <SEP> 90
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Diglycol <SEP> dimethyl <SEP> ether <SEP> 323 <SEP> 100
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Dimethyl <SEP> Acetamide <SEP> 936 <SEP> 291
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> N,

  N-dimethylformamide <SEP> 1077 <SEP> 334
<tb>
 
The results show that the solvents of the present invention increase the oxidation rate by about 300 times relative to methanol and about 3 to 9 times relative to solvents of the ether type.



   Example 6
To demonstrate the effectiveness of the various solvent-based systems for isomerization, 20 cc samples of 2-methylpentene-1 were subjected to isomerization at 55 ° C and atmospheric pressure. The following results show the conversion of olefins with 200 cc of various solvents.

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    TABLE V
 EMI18.1
 
<tb> Solvent <SEP> Constant <SEP> Dielectric <SEP> Molarity <SEP> of <SEP> the <SEP> Base <SEP> Conversion <SEP> of Olefins
<tb>
 
 EMI18.2
 ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯25 "C¯¯¯¯¯¯¯¯ in Solvent E isom., Min
 EMI18.3
 
<tb> (tertiary butylate <SEP>
<tb> of <SEP> K)
<tb> Hexamethyl <SEP> phosphoramide <SEP> 36 <SEP> 0.91 <SEP> 5 <SEP> x <SEP> 10-2
<tb> "<SEP> 36 <SEP> 0.481 <SEP> 17.7 <SEP> x <SEP> 10-3
<tb> Tetramethyl <SEP> urea <SEP> 24 <SEP> 1.0 <SEP> 4 <SEP> x <SEP> 10-4
<tb> Tetrahydrofuran <SEP> 3 <SEP> 1.0 <SEP> 0
<tb> Alcohol
<tb> / Butyl <SEP> tertiary <SEP> 8 <SEP> 1.0
<tb>
 

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The foregoing results clearly show the increased rate of isomerization obtained with the improved solvent-base system of the present invention.

   Tetrahydrofuran and tertiary butyl alcohol, which are the solvents employed heretofore, do not give conversion, while high conversions are obtained with the solvents defined by the invention.



   Example7
To show that other olefins can be easily isomerized, 20 cc of pentene-1 was contacted.
 EMI19.1
 with a system of hexamethyl 3A) tertiary potassium hosphoramlde-butoxide. 200 cc of the solvent was used and the base molarity was 0.910. The olefin conversion rate (K isom., Min-1) was 6.3 x 10-3.



    Example 8
That an improved rate of isomerization can be obtained using a heavy alkali metal base is illustrated by the results of the following table. The olefin used was 10% 2-methylpentene-1. 100 ml of solvent and 0.4 molar base were used.

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    TABLE VI
 EMI20.1
 
<tb> Solvent <SEP> Butylate <SEP> ter- <SEP> Butylate <SEP> ter- <SEP> Butylate <SEP> of <SEP> Butylate <SEP> tertiary <SEP> of <SEP> Na <SEP> tiary <SEP> of <SEP> K <SEP> Rb <SEP> tiary <SEP> of <SEP> Co
<tb> Hexamethyl
<tb> phosphoramide <SEP> 6 <SEP> x <SEP> 10-5 <SEP> 1.7 <SEP> x <SEP> 10-3 <SEP> 5.6 <SEP> x <SEP> 10-3 <SEP> 10.4 <SEP> x <SEP> 10-3
<tb> Tetramethyl <SEP> -4 <SEP> -4
<tb> urea- <SEP> 0.286 <SEP> x <SEP> 10-4 <SEP> 2.1 <SEP> x <SEP> 10 <SEP> 9.2 <SEP> x <SEP> 10 <SEP>
<tb> Diethyl
<tb> dimethyl <SEP> urea <SEP> - <SEP> - <SEP> 3 <SEP> x <SEP> 10-5 <SEP> 8.6 <SEP> x <SEP> 10-5 <SEP>
<tb>
 

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 Example 9
The following experiments were carried out to demonstrate the oxidation of alkyl aromatics with the base-solvent system of the invention.

   All preparations were made in a nitrogen-dried apparatus, using 100 milliliters of hexamethyl phosphoramide and substantially alcohol-free potassium tertiary butoxide as the base.



  Half the required volume of the base was poured into a glass stopper graduated cylinder and the base was added slowly with continuous shaking to increase the solubility. As the limit of the base solubility was approached, the remainder of the solvent was added and the process was repeated until the specific amount of base was dissolved in the solvent. The required amount of the reaction mixture, i.e. an alkyl aromatic, was placed in a heavy-walled flask. The flask was first flushed with nitrogen. The homogeneous solvent-base solution, previously prepared, was then poured into the reaction flask and an atmosphere of oxygen then removed the nitrogen.

   The entire reaction mixture was allowed to stand (no stirring) until equilibrium was reached.



  At this time, a magnetic stirrer was turned on to start the experiment. At the end of the reaction, the mixture was poured onto 100 g of ice which hydrolyzed the remaining potassium tertiary butoxide. The diluted mixture was subjected to analysis as follows. The reaction mixture plus water was first extracted with 25 ml of normal heptane to extract the unreacted aromatics. The raffinate portion was then extracted ten times with 20 ml of cyclohexane and an aqueous phase and a hydrocarbon phase were recovered, the latter phase containing additional unreacted aromatics. The aqueous phase

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 containing the solvent (hexamethyl phosphoramide) e + of the salts was then extracted with caustic soda and ether.

   The ethereal phase contained the solvent, while the aqueous phase contained the salts. The salts were then treated with HCl and extracted with ether. The aqueous phase from the ether extract contained free carboxylic acid. By steaming, the ether was removed and the solid carboxylic acid was obtained. The following table summarizes the results obtained with five different treatments.

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    TAELEAU VII Summary of the oxidation treatments of alkyl benzene.
 EMI23.1
 
<tb>



  Food
<tb> Toluene, <SEP> gr. <SEP> - <SEP> - <SEP> 2.20 <SEP> 2.23 <SEP> 2.22
<tb> X, ylène, <SEP> br. <SEP> 1.46 <SEP> 1.48 <SEP> - <SEP> - <SEP> Butylate <SEP> tertiary <SEP> of <SEP> K, <SEP> gr. <SEP> 7.5 <SEP> 7.5 <SEP> 5.0 <SEP> 7.5 <SEP> 15.0
<tb> Solvent <SEP> -------------- <SEP> 100 <SEP> ml. <SEP> hexamethyl <SEP> phosphoramide <SEP> --- Pressure <SEP> of <SEP> 02 '<SEP> Atm. <SEP> -------------------- 1 -------------------------- ---- Temperature, <SEP> C. <SEP> 25 <SEP> 80 <SEP> 25 <SEP> 25 <SEP> 25
<tb> Duration, Hours <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 20
<tb> Analysis <SEP> of the <SEP> Product
<tb> Material <SEP> of <SEP> starting <SEP> not <SEP> oxidized, <SEP> gr. <SEP> 0.93 <SEP> - <SEP> 1.38 <SEP> - <SEP> Carboxylic acid <SEP> <SEP> gr.

   <SEP> 0.60 * <SEP> 0.77 * <SEP> 0.70 <SEP> 0.84 <SEP> 1.0
<tb> Conversion, <SEP> moles <SEP>% <SEP> 27 <SEP> 35 <SEP> 24 <SEP> 29 <SEP> 34
<tb> Selectivity, <SEP>% <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
<tb>
   x Recent work has shown that these yields are lowered by around 33%.

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  When toluene was reacted, the product was benzoic acid. When xylene was reacted, the product was phthalic acid. It will be appreciated that the reaction is remarkably selective for the particular carboxylic acid, and that yields of up to 35 moles are obtained; %.



  It should also be noted that by raising the temperature from 25 to 80 ° C., markedly improved yields of phthalic acid were obtained. A treatment essentially similar to the first toluene treatment (central column Table 7) was also carried out. However, the product was analyzed after 6 1/2 hours. The yield of benzoic acid was found to be 17.07%.
 EMI24.1
 Example 10
To show the advantages of the present invention over common hydroxy solvents, the following experiment was carried out. 0.024 moles of toluene was reacted with a base-solvent system comprising 0.09 moles of potassium tertiary butoxide and 100 ml of tertiary butyl alcohol.

   The temperature was maintained at 25 ° C and a pressure of 1 atmosphere of oxygen was provided in the reaction flask, in a manner similar to that described in Example 9. After 20 hours, the contents of the flask were analyzed and the reaction flask was tested. found that there was no / conversion of toluene to benzoic steel.
 EMI24.2
 Example 11
To demonstrate the use of the present invention in the formation of carbene, the following experiment was carried out. Methyl chloride was added to a flask containing potassium tertiary butoxide in hexamethyl phosphoramide at room temperature. Cyclohexane was added to trap the carbene formed. The following table gives the reagents used and the products formed.

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  TABLE VIII
 EMI25.1
 
<tb> Solvent, <SEP> 300 <SEP> ce <SEP> of hexamethyl <SEP> phosphoramide
<tb>
<tb> Base <SEP> KOTBu <SEP> 18.5 <SEP> gr
<tb>
<tb> Temperature, <SEP> C <SEP> 25
<tb>
<tb> CH3C1 <SEP> 7,58 <SEP> gr
<tb>
<tb> Cyclohexene <SEP> 114.5 <SEP> gr
<tb>
<tb> Products
<tb>
<tb> t-Butyl <SEP> Methyl <SEP> ether <SEP> 59.36%
<tb>
<tb> T-Butyl <SEP> <SEP> 21.47%
<tb>
<tb> Norcarane <SEP> * <SEP> 4.40%
<tb>
<tb> C9 + <SEP> 14.77%
<tb>
 *
As will be noted, there was a 4.4% norcaran formation. The products were analyzed by gas-liquid separation chromatography. This experiment represents the first production of norcarane by methyl chloride in relatively high yields.

   Previously, norcarane was produced by decomposing diazomethane, which was an expensive technique.
 EMI25.2
 Example 12 1-x- e-, Lal) 1 - 1?
In a similar manner to that described in Example 11, a carbene was produced from chloroform according to the following reaction:
 EMI25.3
 + CH 3C '# ss # + Kci + H20 0 3 HMPA C7 KOI ## Temp. ambient
The reaction was carried out at room temperature using the weak base (caustic potash) dissolved in hexamethyl phosphoramide. A yield of 25% was obtained.

 <Desc / Clms Page number 26>

 



    Example 13
The oxidation of sulphurous compounds is of prime importance in softening petroleum feedstocks. To show the oxidation of mercaptans to their corresponding sulfonic acids, the following experiment was carried out.



  The reaction was carried out in a stirred glass flask containing the solvent-base and the mercaptan.



  Constant pressure (atmospheric pressure) of oxygen was applied to the vial. At the end of the treatment, the entire product was neutralized with HCl and analyzed. The following table shows the quantities of materials used and the product obtained in the two treatments.



   TABLE IX
Sulfonic acids
25 C, atmospheric pressure Reagents n-Butyl mercaptan, moles 0.1 O2 maintenance of a pressure of o2 of 1 atmosphere Solvent ce Hexamethyl phosphoramide 83 Methanol 10 Base, moles Sodium methylate 0.2 - Caustic soda - 0.2 Duration , minutes 418 RSH conversion approx. 100% Product n-butyl sulfonic acid approx. 90% It should be noted that an almost total conversion of the mer-captans was obtained and that about 90% of the corresponding sulfonic acid was / formed

 <Desc / Clms Page number 27>

 
 EMI27.1
 Example 14 E: J:

  ¯! 1-
Polymerization of olefins can be easily accomplished using butyl lithium dissolved in hexamethyl phosphoramide. 150 cc of butadiene was dissolved with 400 cc of hexamethyl phosphoramide containing 20 g of butyl lithium at room temperature. Full conversion to polymer was achieved within seconds.



   Example 15
25 g of benzyl potassium were dissolved in 200 cc of hexamethyl phosphoramide. The solution was placed under a pressure of 700 pounds of ethylene. It was found that 10 moles of ethylene were absorbed for each mole of benzyl potassium. The product, not yet conclusively analyzed, obtained after analysis consisted of 52 grams of viscous liquid.



   Example 16
To show the improved stability to oxidation, compared to solvents comprising hydrogen atoms on the dipole atom or on the adjacent atom of the dipole atom, solvents not comprising a hydrogen atom, the following solvent-base systems were subjected to a pressure of 1 atmosphere of oxygen.
 EMI27.2
 
<tb>



  Solvent, <SEP> Base, <SEP> Duration, <SEP> O2 <SEP> absorbed,
<tb>
<tb>
<tb>
<tb> Balance <SEP> Low., <SEP> gr. <SEP> min. <SEP> O2 <SEP> liters
<tb>
<tb>
<tb> Treatment <SEP> N, N-dimethyl <SEP> Butylate <SEP> ter- <SEP> 45 <SEP> 0.628
<tb>
<tb>
<tb> n 1 <SEP> formamide, <SEP> 100 <SEP> tiary <SEP> of <SEP> K <SEP> 45 <SEP> 0.628
<tb>
<tb>
<tb> 10.3
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Treatment <SEP> Hexamethyl <SEP> phos- <SEP> Butylate <SEP> ter- <SEP> 60 <SEP> 0.027
<tb>
<tb>
<tb>
<tb> n 2 <SEP> phoramide, <SEP> 100 <SEP> tiary <SEP> of <SEP> K <SEP> 0.027
<tb>
<tb>
<tb> 7.5
<tb>
 
The amount of O 2 absorbed is a measure of the oxidative stability of the solvent in the presence of a base.

   It will be noted that in treatment 1 the dimethyl formamide, HCOn (CH3) 2 'which has a hydrogen atom attached to the carbonyl radical dipo-

 <Desc / Clms Page number 28>

 The air absorbed more oxygen than hexamethyl phosphoramide, which has no hydrogen atoms on the phosphoryl radical or on adjacent atoms.



   Example 17
Lithium, sodium, potassium and rubidium were dissolved in hexamethyl phosphoramide. 0.081 moles of 2-methylpentene-1 was introduced into 100 cc of the 93.5 F solution at a pressure of one atmosphere. The concentration of olefins was 0.736 molar. The reaction rates are given in the following table. By way of comparison, the alkali metals were also introduced into dimethyl sulfoxide and tertiary butyl alcohol. Further, the results obtained with the alkali metal catalyst are given in comparison with those obtained with potassium tertiary butoxide.

 <Desc / Clms Page number 29>

 



    TABLE X Conversion Rate (Kmin-1 x 103)
 EMI29.1
 
<tb> Conc. <SEP> Hexamethyl <SEP> Tallow <SEP> oxide <SEP> of
<tb> Catalyst <SEP> Molarity <SEP> Temp. <SEP> F. <SEP> phosphoramide <SEP> Dimethyl <SEP> t-butanol
<tb> Li # <SEP> 2.5 <SEP> 93.5 <SEP> 5900 <SEP> decomposition <SEP> decomposition
<tb> Na # <SEP> 0.178 <SEP> "<SEP> 5900 <SEP>" <SEP> "
<tb> K <SEP> 0.430 <SEP> 24 <SEP> "<SEP>"
<tb> Rb <SEP> 0.0069 <SEP> "<SEP> 10 <SEP>" <SEP> "
<tb> Butylate <SEP> tertiary <SEP> of <SEP> K <SEP> 1.42 <SEP> 131- <SEP> 5.4 <SEP> 0
<tb> Butylate <SEP> tertiary <SEP> of <SEP> K <SEP> 0.48 <SEP> 131 <SEP> 1.7 <SEP> "
<tb>
   # Cis and trans 4-methylpentene-2 and 4-methylpentene-1 appeared in relatively large conversions.

 <Desc / Clms Page number 30>

 



  The foregoing results show that the conversion rates with the solvent to alkali metal system are far superior to those obtained with potassium tertiary butoxide. It should be specially noted that remarkable results are obtained when the lightest alkali metals are used, i.e. lithium and sodium. Both dimethyl sulfoxide and tertiary butyl alcohol / decomposed upon introduction of the alkali metal.



   Example 18
In this example, 2.5 cc of 2-methyl-pentene-1 were introduced in solvents containing 0.5 g of sodium at temperatures of 55 ° C. for two hours. The effect of the solvent system is shown in the following table. In the first treatment 25 cc of hexamethyl phosphora-aid was used; in the second treatment 50 cc of hexamethyl phosphoramide was used and in the third treatment 25 cc of hexamethyl phosphoramide and 250 cc of tetrahydrofuran were used.

 <Desc / Clms Page number 31>

 



    TABLE XI ISOMERIZATION OF OLEFINS
 EMI31.1
 
<tb> Solvent, <SEP> ce.¯¯¯¯¯¯¯
<tb> Hexamethyl <SEP> Tetrahydro <SEP> 2-methyl <SEP> 2-methyl <SEP> trans-4-methyl <SEP> cis-4-methyl <SEP> 4-methyl
<tb> phosphoramide <SEP> furan <SEP> pentene-1 <SEP> pentene-2 <SEP> pentene-2 <SEP> pentene-2 <SEP> pentene-1
<tb> 25 <SEP> 0 <SEP> 8.93 <SEP> 82.41 <SEP> 7.04 <SEP> 1.43 <SEP> 0.29
<tb> 50 <SEP> 0 <SEP> 9.15 <SEP> 77.84 <SEP> 10.94 <SEP> 1.71 <SEP> 0.31
<tb> 25 <SEP> 250 <SEP> 29.68 <SEP> 62.17 <SEP> 7.04 <SEP> 0.97 <SEP> 0.20
<tb>
 

 <Desc / Clms Page number 32>

 The preceding results show the molar percentage of 2-methylpentene-1 and the various reaction products at the end of the two treatments. On increasing the amount of hexamethyl phosphoramide, only a slight change in the reaction products is noted.

   When adding the tetrahydrofuran, it is noted that the reaction proceeds but at a slower rate. Tetrahydrofuran, which would be ineffective if used alone, simply serves as a diluent.



   Example µ
The following results show the ethylation of toluene with the solvent system of the present invention. In Table XII lithium is used as a catalyst and in Table XIII sodium is used.

 <Desc / Clms Page number 33>

   TABLE XII ETHYLATION OF TOLUENE
 EMI33.1
 
<tb> Temperature <SEP> - <SEP> 76 F.
<tb>



  Solvent- <SEP> 350 <SEP> ml <SEP> of hexamethyl <SEP> phosphoramide
<tb> Load- <SEP> 50 <SEP> ml <SEP> of <SEP> toluene
<tb> Catalyst <SEP> - <SEP> 1.7 <SEP> g <SEP> of <SEP> lithium
<tb> Pressure- <SEP> Ethylene, <SEP> 450-500 <SEP> pounds <SEP> per <SEP> inch <SEP> square
<tb> Duration, <SEP> Min.

   <SEP> Toluene <SEP> n-propyl <SEP> benzene <SEP> 3-phenyl <SEP> benzene <SEP> 3-ethyl-3-phenyl <SEP> benzene
<tb> (moles <SEP>%) <SEP> (moles <SEP>%) <SEP> (moles <SEP>%) <SEP> (moles <SEP>%)
<tb> Power supply <SEP> 99.81 <SEP> 0.08 <SEP> 0.04
<tb> 3 <SEP> 99.39 <SEP> 0.52 <SEP> 0.04
<tb> 6 <SEP> 86.42 <SEP> 10.27 <SEP> 3.14
<tb> 9 <SEP> 75.61 <SEP> 17.28 <SEP> 6.27
<tb> 15 <SEP> 51.49 <SEP> 20.01 <SEP> 27.86 <SEP> -
<tb> 21 <SEP> 46.81 <SEP> 20.22 <SEP> 31.52 <SEP> 0.36
<tb> 27 <SEP> 35.41 <SEP> 17.53 <SEP> 45.29 <SEP> 0.60
<tb> 33 <SEP> 32.78 <SEP> 16.97 <SEP> 48.72 <SEP> 0.50
<tb> 39 <SEP> 28 <SEP> 51 <SEP> 17.05 <SEP> 52.77 <SEP> 0.65
<tb> 45 <SEP> 23 <SEP> 58 <SEP> 16.55 <SEP> 57.74 <SEP> 0.96
<tb> 60 <SEP> 24.67 <SEP> 14.86 <SEP> 58.30 <SEP> 0.67
<tb> 90 <SEP> 23.94 <SEP> 13.29 <SEP> 60.63 <SEP> 0.73
<tb> 120 <SEP> 19.31 <SEP> 15.73 <SEP> 62.34 <SEP> 0,

  95
<tb>
 

 <Desc / Clms Page number 34>

   TABLE XIII Solvent- 150 ce. of hexamethyl phosphoramide Charge- 50 cc. of Toluene Catalyst - 5 g Sodium Pressure - Ethylene, 500-600 pounds per square inch
 EMI34.1
 
<tb> Duration <SEP> Temp. <SEP> F. <SEP> Toluene <SEP> n-propyl <SEP> benzene <SEP> 3-phenyl <SEP> benzene <SEP> 3-ethyl-3-phenyl <SEP> benzene
<tb> (moles <SEP>%) <SEP> (moles <SEP>%) <SEP> (moles <SEP>%) <SEP> (moles <SEP>%)
<tb> 1) <SEP> 5 <SEP> min. <SEP> 76 <SEP> 88.07 <SEP> 5.74 <SEP> 6.08--
<tb> 2) <SEP> 2 <SEP> hrs. <SEP> 302 <SEP> 2.9 <SEP> 12.4 <SEP> 77.6 <SEP> 2.7
<tb> 3) <SEP> 6.5 <SEP> hrs. <SEP> "<SEP> 3.88 <SEP> loti./ <SEP> 73.44 <SEP> 6.16
<tb> 4) <SEP> 24 <SEP> hrs. <SEP> "<SEP> 2.8 <SEP> 11.2 <SEP> 78.5 <SEP> 2.9
<tb>
   1, 3 - Analysis by gas chromatography.



  2, 4 - Analysis by mass spectrophotometry.

 <Desc / Clms Page number 35>

 



  The foregoing tables show that when lithium and sodium were used as catalysts in hexamethyl phosphoramide, rapid rates of conversion to normal propyl benzene, 3-phenyl-benzene and 3-ethyl-3- phenyl benzene are obtained.
 EMI35.1
 



  Example 20 Exe, LaL) l¯? 2
The following two treatments were carried out to show the dimerization of ethylene using a sodium-hexamethyl phosphoramide system. In Table XIV below, three product analyzes are given. In process 62 the product was analyzed before adding water to the liquid product. In process 72 the analysis was carried out both before and after the addition of methanol to the liquid mixture.

 <Desc / Clms Page number 36>

 



    TABLE XIV DIMERIZATION OF ETHYLENE
 EMI36.1
 
<tb> Processing <SEP> 62 <SEP> 72
<tb> Solvent <SEP> ----- <SEP> 200 <SEP> cc <SEP> of <SEP> HMPA <SEP> ----- Temperature, <SEP> F. <SEP> 300-320 < SEP> 60-75
<tb> Pressure <SEP> 600-700 <SEP> l.p.p.c. <SEP> 300-450 <SEP> l.p.p.c.
<tb>



  Duration <SEP> 21 <SEP> hours <SEP> l. <SEP> p.p.c. <SEP> 4 <SEP> hours <SEP> l. <SEP> p.p.c.
<tb>



  Catalyst <SEP> 5 <SEP> gm <SEP> of <SEP> sodium <SEP> (0.23 <SEP> M) <SEP> 3 <SEP> gm <SEP> of <SEP> sodium <SEP> (0 , 13 <SEP> M)
<tb>
 
 EMI36.2
 Products, Gas. ----------------------- Moles -------------------
 EMI36.3
 
<tb> 1 <SEP> 2
<tb> H2 <SEP> 0.12 <SEP> 0.31 <SEP> 11.78
<tb> CH4 <SEP> 0 <SEP> 0 <SEP> 1.02
<tb> Ethane <SEP> 0.34 <SEP> 0 <SEP> 18.94
<tb> Ethylene <SEP> 80.88 <SEP> 99.16 <SEP> 55.21
<tb> Butane <SEP> 14.77 <SEP> 0.47 <SEP> 9.76
<tb> Butene <SEP> 0 <SEP> 0.02 <SEP> 0.63
<tb> Pentene <SEP> 0.42 <SEP> 0.01 <SEP> 0
<tb> Pentane <SEP> 3.41 <SEP> 0.02 <SEP> 2.02
<tb> Moles <SEP> collected, <SEP> gas. <SEP> 1.4 <SEP> 1.2 <SEP>, 05
<tb>
   Insoluble matter ------- Traces G. C.

   C6, C8, C10, C12 present --- Treatment 62 - Products before addition of H20 to the liquid product Treatment 72-2 - Products after addition of CH3OH to the liquid mixture, forming an alkyl metal compound.

 <Desc / Clms Page number 37>

 



  The preceding table shows that a significant part of the ethylene was dimerized to butane. This was especially apparent with the addition of methanol in process 72.



   Example 21
In the following experiment. butadiene was polymerized in the presence of lithium and sodium, dissolved in hexamethyl phosphoramide. Normal pentane was added in the first process, this pentane simply acting as an inert solvent.

 <Desc / Clms Page number 38>

 



    TABLE XV POLYMERIZATION OF BUTADIENE
 EMI38.1
 
<tb> Duration <SEP> Tempera- <SEP> Pressure <SEP> Catalyst <SEP> Grams <SEP> Hexamethyl <SEP> n-pentane <SEP> Butadiene <SEP> PolybutaHrs. <SEP> ture, <SEP> F. <SEP> phosphora- <SEP> ce. <SEP> this. <SEP> diene
<tb> mide, <SEP> cc. <SEP> Product,
<tb>
 
 EMI38.2
 ############################# ¯¯¯¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯ ¯ ¯¯¯¯¯¯¯¯¯ Rm.
 EMI38.3
 
<tb>



  24 <SEP> 0 <SEP> - <SEP> 10 <SEP> 1 <SEP> atm. <SEP> Li <SEP> 0.4 <SEP> 20 <SEP> 400 <SEP> 200 <SEP> 170
<tb> "<SEP> 212 <SEP> 20 <SEP> atm. <SEP> Na <SEP> 2 <SEP> 350 <SEP> - <SEP> 86 <SEP> 55
<tb>
 

 <Desc / Clms Page number 39>

 The foregoing results show that satisfactory polymerization of butadiene was obtained using the system of the present invention, the best results being obtained with the lithium catalyst.
 EMI39.1
 Example 22 ExeLnpl2¯2?
The following results show that the solution of alkali metal compounds enhances the organic / organometallic reactions. Two treatments were carried out using potassium dissolved in hexamethyl phosphoramide with benzyl chloride as feed.

   After 12 hours, the reaction mixture was cooled with water and subjected to gas chromatographic analysis. Table XVI gives the results obtained.



   TABLE XVI
Preparation of organometallic compounds
 EMI39.2
 
<tb> Temperature <SEP> 70-80 F
<tb>
<tb> Duration <SEP> 12 <SEP> hours <SEP>
<tb>
<tb>
<tb>
<tb> <SEP> container in <SEP> glass, <SEP> with <SEP> stirrer, <SEP> tablecloth <SEP> of <SEP> N2
<tb>
<tb> 1179-78 <SEP> 1 <SEP> 2
<tb>
<tb>
<tb> Hexamethyl <SEP> phospho-
<tb>
<tb> ramide, <SEP> cc <SEP> 100
<tb>
<tb>
<tb> K, <SEP> grams <SEP> 1.5 <SEP> 3, <SEP> 0 <SEP>
<tb>
<tb>
<tb> <SEP> Benzyl <SEP>, <SEP> gr <SEP> 4.4 <SEP> 5.0
<tb>
<tb>
<tb> Toluene, <SEP> moles <SEP> 12 <SEP> 5.6
<tb>
 
Note that a significant amount of benzyl chloride was converted to toluene. On the addition of benzyl chloride to the solvent system, benzyl potassium was formed.

   By cooling the reaction product with water, toluene and caustic potash are produced.



   Example 23
About 0.2 g of potassium was dissolved in 10 cc of tetramethyl urea. 4 cc of 2-methylpentene-1 was added to

 <Desc / Clms Page number 40>

 Room temperature. After one hour analysis showed 40% conversion to 2-methylpentene-2.



    CLAIMS
1. A process for carrying out conversion reactions of organic compounds, which comprises: contacting an organic compound comprising a weakly ionizable carbon-hydrogen bond with a base-solvent system, wherein the solvent is an aprotic liquid free of hydroxy groups and having a dipole radical and a dielectric constant exceeding 15 to 25 ° C, or with a solvent-alkali metal system further characterized in that the dipolar radical and the neighboring atoms of the radical dipolar are free from hydrogen, forming a carbaion intermediate and reacting this intermediate to form a product.


    

Claims (1)

2. A process according to claim 1, in which a base is used and the solvent is further characterized in that the dipole radical and the neighboring atoms of this dipole radical are free from hydrogen. 3. A process according to claim 1 which comprises contacting an organic compound with a solvent-alkali metal system, wherein the solvent has the formula: EMI40.1 wherein Y is selected from the group consisting of oxygen, nitrogen, and sulfur, R is selected from the group consisting of alkyl and aryl radicals and n is the valence of Y. 4. A process according to claim 3 which comprises contacting an organic halide with the solvent-alkali metal system to form an organometallic compound. <Desc / Clms Page number 41> 5. The process of either of claims 1 and 2, wherein the solvent has a dipolar radical selected from the group consisting of carbonyl, phosphoryl, sulfinyl, sulfonyl and thiocarbonyl radicals. 6. The process of claims 1 or 2, wherein the base is an aloaline metal alkoxide. 7. The process of claim 6, wherein the alkali metal is selected from the group consisting of cesium, rubidium and potassium. 8. The process of claims 1 or 2, wherein the conversion reaction is isomerization and the organic compound is an unsaturated hydrocarbon. 9. The process of claims 1 or 2, wherein the conversion reaction is side chain alkylation and the organic compound is an aromatic. 10. The process of claims or 2, wherein the conversion reaction is carboxylation. 11. The process of claims 1 or 2, wherein the conversion reaction is a condensation. 12. The process of claims 1 or 2, wherein the conversion reaction is a polymerisatic and the organic compound is an unsaturated hydrocarbon selected from the group consisting of olefins, diolefins and aromatics having an unsaturated side chain. 13. The process of claims 1 or 2, wherein the conversion reaction is carbonylation and the organic compound is an unsaturated hydrocarbon. 14. The process of claims 1 or 2, wherein the conversion reaction is formation of carbene. 15. The process of claims 1 or 2, wherein the conversion reaction is homogeneous hydrogenation and the organic compound is an unsaturated hydrocarbon. <Desc / Clms Page number 42> 16. The process of claims 1 or 2, wherein the conversion reaction is hydroboration and the organic compound is an olefin. 17. The process of claims 1 or 2, wherein the conversion reaction is benzyne formation. 18. The process of claim 2, wherein the conversion reaction is an oxidation of mercaptan. 19. The process of claims 1 or 2, wherein the conversion reaction is silene formation. 20. The process of claim 2, wherein the conversion reaction is oxidation. 21. The process of claims 1 or 2, wherein the conversion reaction is the formation of organometallic compounds. 22. The process of claims 1 or 2, wherein the conversion reaction is the formation of vinyl ethers. 23. An improved solvent-base system useful for the process of claim 1, wherein the solvent is an aprotic dipolar liquid free of hydroxy groups and having a dielectric constant exceeding 15 to 25 ° C, and wherein the base is an alkoxide. alkali metal, said alkali metal having an atomic number of at least 37. 24. An improved solvent-base system useful for the process of claim 1, wherein the solvent is dimethyl sulfoxide and the base an alkali metal alcoholate. 25. An improved solvent-base system useful for the process of claim 1, wherein the solvent is N, N-dimethyl formamide and the base is an alkali metal alcoholate. 26. A liquid composition useful for the process of claim 1, prepared by adding an alkali metal to a liquid, non-hydroxylic, aprotic solvent having a <Desc / Clms Page number 43> dielectric constant of at least 15 to 25 C, and a dipolar radical, this solvent being further characterized in that the dipolar radical and the adjacent atoms of this radical are free from hydrogen. 27. The liquid composition of claim 26, prepared by adding an alkali metal to a compound having the formula: EMI43.1 wherein Y is selected from the group consisting of oxygen, nitrogen and sulfur, R is selected from the group consisting of alkyl and aryl radicals, and n is the valency of Y. 28. The composition of claim 27, wherein the compound is a hexa-alkyl phosphoramide. 29. The composition of claim 27, wherein the compound is normal trialkyl phosphate. 30. The composition of claim 27, wherein the compound is trialkyl trithiophosphate. 31. A liquid composition according to claim 26 prepared by adding an alkali metal to hexamethyl phosphoranide. 32. A liquid composition according to claim 26, prepared by adding an alkali metal to tetramethyl urea. 33. The composition of claim 31, wherein the alkali metal is lithium. 34. An improved base-solvent system useful for the process of claim 1 which comprises: a base, (2) a non-hydroxylic, aprotic liquid solvent having a dielectric constant of at least 15 to 25 C and a di-polar radical, this solvent being further characterized in that the <Desc / Clms Page number 44> Dipolar radicals and the adjacent atoms of these radicals are free of hydrogen. 35. The composition of claim 34, wherein the dipolar radical is selected from the group consisting of carbonyl, phosphoryl, sulfinyl, sulfonyl and thiocarbonyl radicals. 36. The improved solvent-base system of claim 34, wherein the base is dissolved in the solvent. 37. The improved solvent-base system of claim 36, wherein at least 10% by weight, preferably 20-40% by weight of the system is firm by base. 38. The improved solvent-base system of claim 35, wherein the base is an alkali metal alcoholate. 39. The improved solvent-base system of claim 38, wherein the alkali metal has an atomic number of at least 19. 40. The improved solvent-base system of claim 39, wherein the alkali metal is cesium. 41. An improved solvent-base system useful for the process of claim 1 which comprises a solvent selected from the group consisting of hexamethyl phosphoramide, tetramethyl urea and bis-dialkyl amino sulfoxides, and a base selected from the group comprising alkali metal hydroxides, alkali metal alcoholates and alkali metal amines.