Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
  • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
  • C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
  • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
  • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
  • C07C2/66—Catalytic processes
  • C07C2/70—Catalytic processes with acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • C07C2527/06—Halogens; Compounds thereof
  • C07C2527/08—Halides
  • C07C2527/12—Fluorides
  • C07C2527/1206—Hydrogen fluoride

Definitions

• the invention relates to methods for producing arylalkanes and alkylphenols having a relatively low content of isomers in which the aromatic substituent is in the 2 position on the alkyl chain.
• an alkylation product is usually obtained which has a relatively low content of isomers in which the aromatic group is positioned near one end of the alkyl chain but
• the alkylation product normally has a content of isomers in which the aromatic substituent is in the 2 position of the alkyl chain which is so high as to make the product less than most desirable for some uses.
• the parafiin diluent can suitably be added to the reactor simultaneously with the reactants and can be recovered in the distillation operation conventionally performed subsequent to the alkylation so that the process does not require any additional process step and does not result in the consumption of a substantial quantity of any additional raw material.
• paraffin material can suitably be employed in the process of this invention and one can use straight chain parafiins, branched chain paraflins, or cyclo-paraflins alone or in admixture with each other.
• Straight chain paraflins and unsubstituted cyclo-paraflins are preferred because the presence of a secondary or tertiary carbon atom in the paraffin increases its reactivity in the presence of HF and can under adverse conditions result in undesired side reactions.
• the choice between straight chain paraffins and unsubstituted cyclo-parafiins is dictated largely by availability, but in some instances, the boiling point or solubility of the paratfin in the reactants will have a bearing upon ones choice.
• a parafiin material be selected which has a boiling point different from that of the aromatic reactant used in the manufacture of the arylalkane product and different from that of any of the isomers normally present in the reaction product so that the parafiin material can readily be recovered for reuse by distillation. Also, it is desirable to select a paraifin material that is readily soluble at the selected level of use in the raw material mixture and also in the individual reactants so that the formation of a separate parafiin phase is avoided. The latter consideration presents no real problem since almost all paraffin materials are miscible with the usual alkenes and aromatic hydrocarbons utilized in the production of arylalkane and alkylphenol detergent intermediates.
• the chain length or number of carbon atoms in the paraflin material is of little or no importance as long as the paraffin material has the desired physical characteristics because, as set forth above, the parafiin is normally inert in the reaction mixture and is recovered unchanged upon the completion of the reaction.
• a paraflin should be selected which has a boiling point at least as high as the maximum reaction temperature to be employed but not so high that it cannot be recovered from the high boiling still bottoms by distillation.
• a chain length can be selected to provide a boiling point different from that of the unreacted raw material and any of the desired isomers of the product to facilitate recovery of the paraflin material.
• the reaction is to be conducted at a very low temperature and/or under pressure, it is possible to employ a material having as few as 4 carbon atoms such as nbutane or cyclobutane.
• a material having as few as 4 carbon atoms such as nbutane or cyclobutane.
• paraffins having as many as about 32 carbon atoms as illustrated by petroleum waxes although in some instances solubility and recovery problems are encountered when employing such materials.
• it is preferred to use a paraflin material having from 5 to 15 carbon atoms and illustrative examples of preferred materials include n-hexane, cyclo-hexane, n-heptane, and n-dodecane.
• the amount of paraffin employed has a bearing upon the quantity of 2-arylalkanes or 2-hydroxyarylalkanes in the alkylation product and if one desires only a slight reduction in the content of such isomers in the product, it is only necessary in accordance With this invention to employ as little as about 5% by weight, based upon the weight of alkene reactant, of parafiin. In most instances, however, one will desire a relatively large reduction in the 2-arylalkane or 2-hydroxyarylalkane isomer content of the reaction product and will employ an amount of paraffin equal to at least about 50% by weight, based upon the weight of alkene reactant.
• the preferred amount of paraffin material to be employed is from about 100% to 1000% by weight, based upon the weight of alkene reactant or, in other words, a weight ratio of paraflin to alkene of from about 1: 1 to about 1021.
• the parafiin material is divided into two quantitles and a first portion thereof is mixed with at least a portion of the aromatic reactant, for example from 10% to 100% thereof, and the desired quantity of HF catalyst.
• the second portion of the parafiin material is then mixed with the alkene reactant and the remainder, if any, of the aromatic reactant.
• the two mixtures are then mixed together over a period of time preferably with constant agitation to eliminate the possibility of localized concentration of reagents and undesired temperature gradients within the reaction mixture.
• the portions of the paraffin material be approximately equal, and if the paraffin is divided into unequal proportions, the larger proportion should be added to the catalyst containing mixture before the alkene is mixed therewith.
• the parafiin should be added to the catalyst containing mixture but satisfactory results can be obtained by adding 100% of the paraflin to the catalyst mixture or any other percentage as long as the catalyst mixture contains an amount of paratlin equal to about by weight of the alkene reactant at the time mixing of the alkene reactant with the catalyst is initiated.
• the process of this invention can be conventional and can be employed in the production of substantially any arylalkane or alkylphenol product which has been conventionally employed in the manufacture of detergent surface active agents.
• the aromatic hydrocarbon most frequently employed in the manufacture of detergent intermediates is benzene, and the phe nolic compound most frequently employed is phenol.
• other monocyclic aromatic hydrocarbons and phenols can suitably be employed in the process, and suitable examples include resorcinol, ortho-cresol, toluene, xylene, and cumene.
• any aliphatic hydrocarbon substituent group or groups on the aromatic nucleus should in each instance be saturated to prevent side reactions and the total number of substituents, including hydroxy groups, on the aromatic nucleus preferably should not be more than 2 or 3 in number.
• the aromatic reactant will contain not more than about 9 carbon atoms, although this limitation is dictated by availability and desirability for use in the manufacture of detergent intermediates, and if desired, the invention can be used with aromatic reactants containing 12 or 15 or more carbon atoms.
• Straight chain alpha-olefins which can suitably be em ployed in the process of this invention include any of those conventionally employed in the manufacture of detergent intermediates. In most instances, the alpha-olefins will have from 8 to 24 carbon atoms, and alpha-olefins having a molecular chain length of from to 20 carbon atoms are preferred. Commercial alpha-olefins are usually mixtures rather than substantially pure materials and such mixtures having average molecular chain lengths within the above ranges are quite suitable for use in the process of this invention.
• an aromatic to olefin molar ratio of at least about 1:1 because the use of a lower ratio results in excessive formation of high boiling by-products.
• aromatic to olefin molar ratio there is no upper limit as to the aromatic to olefin molar ratio except that dictated by convenience and the economics of recovering unreacted raw materials, and an aromatic to olefin ratio as high as 100:1 can suitably be employed, but the preferred aromatic to olefin ratio is generally from 1 /2:1 to 10:1. Varying the aromatic to olefin ratio in most instances has no marked effect upon the Z-arylalkane or 2-hydroxy arylalkane content of the product but does affect in a conventional manner the nature and amount of by-products produced.
• the amount of catalyst to be employed can be conventional and can range from about 10% by weight, based upon the weight of alkene material in the reaction mix: ture, to an upper limit dictated only by convenience and one can, for example, with satisfactory results, employ an amount of catalyst sufiicient to provide a weight ratio of catalyst to total olefin of as high as 20: 1. If desired, one can even employ in accordance with the procedure described and claimed in United States application, Ser. No.
• a small amount of catalyst for example, as little as 0.2% by weight based upon the over-all weight of the reaction mixture, that a separate catalyst phase is not obtained, but this results in a marked increase in the 2-arylalkane isomer content of the product as compared to the minimum which can be obtained employing the process of the present invention and in most instances is not desirable.
• a preferred amount of catalyst is that which will provide a weight ratio of catalyst to total olefin reactant of from 1:2 to 10: 1.
• the temperature at which the reaction is conducted in accordance with this invention can be conventional, and for example, can range from the freezing point of the reaction mixture to about 200 C. or even higher, but the preferred operating temperature range is from about 10 C. to C. with temperatures of from about 5 C. to 60 C. being especially preferred.
• a change in operating temperature in most instances results in a significant change in the proportion of 2- arylalkane or Z-hydroxyarylalkane isomers in the product with low reaction temperatures favoring decreased amounts of the 2-arylalkane or Z-hydroxyarylalkane isomers in the product.
• a reduction in temperature of from 55 C. to 0 C. can in some instances result in a much as 7% to 8%, based on the over-all weight of the product, reduction in the percent of Z-phenyl isomers in the product.
• the pressure under which the alkylation reaction is conducted can be varied within a wide range as long as the pressure employed is not so low as to result in the vaporization of raw materials or excessive catalyst loss. Suitable operating pressures can vary from about 0.5 to 10 atmospheres with the preferred pressure range being from about 1 to 4 atmospheres.
• EXAMPLE I A mixture of 200 parts of benzene and 200 parts by weight of anhydrous HP is placed in a suitable alkylation apparatus and heated at 55 C. under 40 pounds p.s.i.g. pressure. At a temperature of 55 C., it has been found that the pressure should be maintained at least about 40 p.s.i.g. to avoid catalyst loss. A mixture of parts of alpha-dodecene and 100 parts of benzene is then added with constant agitation over a period of ten minutes, and the reaction mixture is retained for an additional ten minutes at 55 C. with constant agitation. The mixture is then cooled to 6 C. and allowed to stand for one hour after which time the organic layer is separated from the catalyst layer by decantation. The separated organic layer is then distilled to remove unreacted benzene and dissolved HF catalyst and a sample of the thus purified product is analyzed by vapor phase chromotography to determine the isomer distribution.
• Procedure B Procedure For comparative purposes, the procedures of this example were used to alkylate benzene with dodecene-6 and even starting with an olefin in which the double bond is centrally disposed, it was only possible to reduce the 2-phenyldodecane content of the product to 13.6% (14.8% when no n-hexane was employed), thus illustrating that the process of this invention makes possible using pure alpha-olefins or mixtures of alpha-olefins and internal olfeins, results which were heretofore obtainable in a single step process only by using a pure olefin material in which the double bond is centrally disposed with respect to the aliphatic chain.
• Example II By comparing the results obtained in Example I with those obtained in Example II, it will be seen that improved results are obtained using low reaction temperatures.
• EXAMPLE III A mixture of 200 parts by weight of benzene and about 200 parts of anhydrous HF is placed in a suitable alkylation apparatus and heated to 55 C. maintaining a pressure of 40 p.s.i.g. to insure the presence of a liquid HF phase. There is then added to the catalyst mixture over a period of about ten minutes and with constant agitation a mixture containing 25 parts by weight of alphadodecane, 25 parts by weight of alpha-tetradecene, 25 parts by weight of alpha-hexadecene, 25 parts by weight of alpha-octadecene, and 100- parts by weight of benzene.
• alpha-olefin has a molecular chain length of from 10 to 20 carbon atoms.
• reaction temperature is within the range of about -10 C. to C.
• paraflin is a straight chain paraffin having from 5 to 15 carbon atoms.
• a process in accordance with claim 1 wherein a first mixture is formed of at least a portion of said aromatic compound, said H.F. catalyst, and a portion of said paraffin, a second mixture is formed of said alkene reactant, the remainder, if any, of said aromatic compound and a portion of said paraflin, and said mixtures are then mixed together while maintaining the temperature of the resultant mixture within the range of -10 C. to 80 C. and while maintaining the resultant mixture under a pressure of from 0.5 to 10 atmospheres correlated with respect to temperatures to prevent catalyst loss.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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Cited By (5)

Citations (6)

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• 1966
  • 1966-05-26 US US553033A patent/US3483262A/en not_active Expired - Lifetime
• 1967
  • 1967-05-09 IL IL27943A patent/IL27943A/en unknown
  • 1967-05-22 BE BE698779D patent/BE698779A/xx unknown
  • 1967-05-22 LU LU53719D patent/LU53719A1/xx unknown
  • 1967-05-24 DE DE1967M0074084 patent/DE1618703B1/de active Pending
  • 1967-05-24 NL NL6707218A patent/NL6707218A/xx unknown
  • 1967-05-25 GB GB24475/67A patent/GB1191927A/en not_active Expired

Patent Citations (6)

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