US3914272A - Alkyl arylsulfonate exchange process - Google Patents

Alkyl arylsulfonate exchange process Download PDF

Info

Publication number
US3914272A
US3914272A US371230A US37123073A US3914272A US 3914272 A US3914272 A US 3914272A US 371230 A US371230 A US 371230A US 37123073 A US37123073 A US 37123073A US 3914272 A US3914272 A US 3914272A
Authority
US
United States
Prior art keywords
alkyl
sulfonate
halide
process according
arylsulfonate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US371230A
Inventor
Charles M Starks
Jr Owen Portwood
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ConocoPhillips Co
Original Assignee
Continental Oil Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Continental Oil Co filed Critical Continental Oil Co
Priority to US371230A priority Critical patent/US3914272A/en
Application granted granted Critical
Publication of US3914272A publication Critical patent/US3914272A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens

Definitions

  • the invention involves a process wherein the alkyl group of a higher alkyl halide is exchanged with the alkyl group of a lower alkyl arylsulfonate in the presence of an organic quaternary salt.
  • the resulting higher alkyl arylsulfonate product may then be easily hydrolyzed to produce the corresponding higher alkanols.
  • RX The higher alkyl halide which may be used in the invention are described by the formula RX wherein R is a straight or branch chain alkyl having from 6 to 40 carbon atoms and x is a halogen such as bromine, chlorine or iodine.
  • RX a straight or branch chain alkyl having from 6 to 40 carbon atoms and x is a halogen such as bromine, chlorine or iodine.
  • halides are readily obtained by reacting olefins having 6 to 40 carbon atoms with a hydrogen halide such as l-lBr or HCl as is known in the art.
  • alkyl halides described above are hexyl chloride, nonyl chloride, decyl bromide, eicosyl chloride, l-metehylheptadecyl bromide, tetradecyl chloride, nonyl iodide, octyl bromide, 2-ethylhexy1 chloride, nonacosyl bromide, 2-octyldecyl chloride, Z-tetradecylhexadecyl bromide, and the like.
  • the lower alkyl arylsulfonates which are reacted with the above alkyl halides in the exchange process are defined by wherein n is zero or one; R is a halogen, such as bromine or chlorine, or a C to C alkyl group; and R is a C, to C alkyl group.
  • R is a halogen, such as bromine or chlorine, or a C to C alkyl group; and R is a C, to C alkyl group.
  • Illustrative of the lower alkyl arylsulfonates include methyl p-methylbenzene sulfonate, methyl pbromobenzene sulfonate, ethylbenzene sulfonate, butylbenzene sulfonate, propylchlorobenzene sulfonate, ethyl p-methylbenzene sulfonate, ethyl butylbenzene sulfonate, and the like.
  • M is a pentavalent ion of an element selected from the group consisting of nitrogen, phosphorus, arsenic, antimony and bismuth; each of R R R and R is, independently, an alkyl group containing 1 to 30 carbon atoms, a phenyl group, a benzyl group, or an alkyl substituted benzyl group wherein the alkyl group has 1 to 30 carbon atoms; and X is hydroxide or an anion derived from an organic or inorganic acid such as a halide, e.g., bromine or chlorine, sulfate, sulfonate, or acetate.
  • M is nitrogen, phosphorous or arsenic; each of R R R and R are alkyl groups; and X
  • quaternary salts include hexadecyltrihexylammonium bromide, didodecyldimethylammonium chloride, tetraheptylammonium iodide, trioctylethylammoniumbromide, tetranonylammonium hydroxide, tricaprylyldodecylammonium ptoluene sulfonate, tributyldecylphosphonium bromide, tetradodecylphosphonium chloride, triphenyldecylphosphonium chloride, trioctylbenzylammonium bromide, tributyloctadecylphosphonium bromide, tribenzyldecylarsonium chloride, and
  • the exchange process is carried out by bringing together the higher alkyl halide and the lower alkyl arylsulfonate, such as in a reaction vessel, in the presence of the organic quaternary salt.
  • the ratio of the higher alkyl halide to the sulfonate is not critical as the reaction is an equilibrium reaction and will proceed to some extent as long as some of each reactant is present. It is desirable, however, to operate with about a one-to-one molar ratio or with an excess of the sulfonate to drive the reaction toward completion with the greatest conversion of the alkyl halide as is desirable for an overall scheme in producing higher alkanols.
  • the organic quaternary salt should be employed in an amount of at least about 0.01 weight percent based on the total organic reactants, and preferably in an amount in the range of about 0.01 to 10 weight percent.
  • temperatures employed in the exchange process can vary widely, depending on the desired reaction rates as well as the particular organic reactants and the organic quaternary salt. Generally, temperatures in the range of 0C to 200C may be employed. However, as previously indicated and as is understood in the art, the temperatures employed for any specific reaction must take into consideration the decomposition temperatures of the reactants as well as the quaternary salt.
  • the process is preferably carried out with the reactants in the liquid phase.
  • the reactants are liquids at ambient conditions or may be rendered in the liquid phase under reaction conditions.
  • inert solvents may be employed.
  • solvents include such things as hydrocarbons (e.g., benzene, toluene and paraffins), ethers, chloroform and other inert materials capable of dissolving the organic reactants.
  • the higher alkyl arylsulfonate product produced by the alkyl exchange process of this invention is readily hydrolyzed to convert the high alkyl moieties to the corresponding higher alkanols which have a variety of known uses, e.g., solvents, precursors for detergents,
  • EXAMPLE 4 l-methylheptadecyl chloride and ethyl pmethylbenzene sulfonate may be reacted in the presence 'of triberizyldecylarsonium chloride as described I in 'E'xam plej'to effect alkyl'exchange.
  • Alkyl exchange may be effected similarly as described in 'Example 2 by reacting decyl bromide with methylbe'nzene sulfonate in the presence of trioctylethylammonium bromide.
  • a process for exchanging alkyl moieties between 7 compounds which comprises reacting a lower alkyl aryl :sulfonate with a higher alkyl halide at temperatures in :thexrangc of 0C to 200C in the presence of at least 0.01 weight percent of an organic quaternary salt based on the total alkyl halide and alkyl aryl sulfonate; said lower alkyl aryl sulfonate being defined by-the formula Rlln wherein n is zero or one; R is halogen or C to C alkyl group, and R" is a C and C alkyl group; said higher alkyl halide being defined by the formula RX wherein R is. a straight or branch chain alkyl having 6 to 40 carbon atoms and X is chlorine, bromine, or iodine; said alkyl moieties being exchanged being R and R;
  • organic quaternary salt being defined by the formula (R1R2R3R4M X wherein M is a pentavalent ion of an element selected from the group consisting of nitrogen and phosphorus; each of R R R and R independently, is an alkyl group having 1 to 30 carbon atoms, a phenyl group, a benzyl group, or an alkyl substituted benzyl group wherein the alkyl group has 1 to 30 carbon atoms, and X is hydroxide, bromine, chlorine, iodine, sulfate, paratoluene sulfonate or acetate.
  • organic quaternary salt is present in an amount in the range of 0.01 to 10 weight percent based on the alkyl halide and alkyl arylsulfonate.
  • the lower alkyl arylsulfonate is methyl para-methyl benzene sulfonate, methyl para-bromo benzene sulfonate, ethylbenzene sulfonate, butyl-benzene sulfonate, propylchloro-benzene sulfonate, ethyl para-methyl benzene sulfonate, or ethyl butylbenzene sulfonate.
  • a process for exchanging alkyl moieties between compounds which comprises reacting a lower alkyl aryl sulfonate with a higher alkyl halide at temperatures in the range of 0C to 200C in the presence of an inert solvent and at least 0.01 weight percent of an organic quaternary salt based on the total alkyl halide and alkyl aryl sulfonate; said lower alkyl aryl sulfonate being defined by the formula wherein n is zero or one; R is halogen or C to C alkyl group, and R" is a C to C alkyl group; said higher alkyl halide being defined by the formula RX wherein R is a straight or branch chain alkyl group having 6 to 40 carbon atoms and X is chlorine, bromine, or iodine; said alkyl moieties being exchanged being R and R"; said inert solvent being benzene, toluene, paraffin, ether, or chloro

Landscapes

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

Abstract

A process for exchanging alkyl moieties between compounds comprising reacting a lower alkyl arylsulfonate with a higher alkyl halide in the presence of an organic quaternary salt. The process is useful in converting the higher alkyl group of the starting halide to the corresponding alcohols by first employing the process of the invention to convert the higher alkyl group to the corresponding arylsulfonate followed by hydrolysis to produce the higher alkanols.

Description

United States Patent [1 1 Starks et al.
[ Oct. 21, 1975 ALKYL ARYLSULFONATE EXCHANGE PROCESS [75] Inventors: Charles M. Starks, Ponca City,
Okla; Owen Portwood, Jr., Janesville, Wis.
[73] Assignee: Continental Oil Company, Ponca City, Okla.
[22] Filed: July 2, 1973 [21] Appl. No.: 371,230
[52] US. Cl 260/456 P; 260/652 R [51] Int. Cl. C07C 143/68 [58] Field of Search 260/456 P, 456 R [56] References Cited OTHER PUBLICATIONS l-loffmann, J. Chem. Soc., 1965, pp. 6753-6769.
Primary Examiner-Bemard Helfin Assistant ExaminerNicky Chan' Attorney, Agent, or Firm-Cortlah R. Schupbach, Jr.
[5 7 ABSTRACT A process for exchanging alkyl moieties between com- 7 Claims, No Drawings ALKYL ARYLSULFONATE EXCHANGE PROCESS This invention relates to an alkyl exchange process which has utility in an overall scheme for producing alkanols.
Briefly described, the invention involves a process wherein the alkyl group of a higher alkyl halide is exchanged with the alkyl group of a lower alkyl arylsulfonate in the presence of an organic quaternary salt. The resulting higher alkyl arylsulfonate product may then be easily hydrolyzed to produce the corresponding higher alkanols.
The higher alkyl halide which may be used in the invention are described by the formula RX wherein R is a straight or branch chain alkyl having from 6 to 40 carbon atoms and x is a halogen such as bromine, chlorine or iodine. These halides are readily obtained by reacting olefins having 6 to 40 carbon atoms with a hydrogen halide such as l-lBr or HCl as is known in the art.
Illustrative of suitable alkyl halides described above are hexyl chloride, nonyl chloride, decyl bromide, eicosyl chloride, l-metehylheptadecyl bromide, tetradecyl chloride, nonyl iodide, octyl bromide, 2-ethylhexy1 chloride, nonacosyl bromide, 2-octyldecyl chloride, Z-tetradecylhexadecyl bromide, and the like.
The lower alkyl arylsulfonates which are reacted with the above alkyl halides in the exchange process are defined by wherein n is zero or one; R is a halogen, such as bromine or chlorine, or a C to C alkyl group; and R is a C, to C alkyl group. These compounds are readily obtained by reaction of C to C lower alkanols with the corresponding arylsulfonyl chloride or arylsulfonic acid.
Illustrative of the lower alkyl arylsulfonates include methyl p-methylbenzene sulfonate, methyl pbromobenzene sulfonate, ethylbenzene sulfonate, butylbenzene sulfonate, propylchlorobenzene sulfonate, ethyl p-methylbenzene sulfonate, ethyl butylbenzene sulfonate, and the like.
The exchange reaction between the above-described reactants is carried out in the presence of an organic quaternary salt such as are described in British Pat. No. 1,227,144. Generally, these salts may be defined by the formula wherein M is a pentavalent ion of an element selected from the group consisting of nitrogen, phosphorus, arsenic, antimony and bismuth; each of R R R and R is, independently, an alkyl group containing 1 to 30 carbon atoms, a phenyl group, a benzyl group, or an alkyl substituted benzyl group wherein the alkyl group has 1 to 30 carbon atoms; and X is hydroxide or an anion derived from an organic or inorganic acid such as a halide, e.g., bromine or chlorine, sulfate, sulfonate, or acetate. Preferably, M is nitrogen, phosphorous or arsenic; each of R R R and R are alkyl groups; and X is a halide.
Some examples of these quaternary salts include hexadecyltrihexylammonium bromide, didodecyldimethylammonium chloride, tetraheptylammonium iodide, trioctylethylammoniumbromide, tetranonylammonium hydroxide, tricaprylyldodecylammonium ptoluene sulfonate, tributyldecylphosphonium bromide, tetradodecylphosphonium chloride, triphenyldecylphosphonium chloride, trioctylbenzylammonium bromide, tributyloctadecylphosphonium bromide, tribenzyldecylarsonium chloride, and
The exchange process is carried out by bringing together the higher alkyl halide and the lower alkyl arylsulfonate, such as in a reaction vessel, in the presence of the organic quaternary salt. The ratio of the higher alkyl halide to the sulfonate is not critical as the reaction is an equilibrium reaction and will proceed to some extent as long as some of each reactant is present. It is desirable, however, to operate with about a one-to-one molar ratio or with an excess of the sulfonate to drive the reaction toward completion with the greatest conversion of the alkyl halide as is desirable for an overall scheme in producing higher alkanols.
The organic quaternary salt should be employed in an amount of at least about 0.01 weight percent based on the total organic reactants, and preferably in an amount in the range of about 0.01 to 10 weight percent.
The temperatures employed in the exchange process can vary widely, depending on the desired reaction rates as well as the particular organic reactants and the organic quaternary salt. Generally, temperatures in the range of 0C to 200C may be employed. However, as previously indicated and as is understood in the art, the temperatures employed for any specific reaction must take into consideration the decomposition temperatures of the reactants as well as the quaternary salt.
The process is preferably carried out with the reactants in the liquid phase. Generally, the reactants are liquids at ambient conditions or may be rendered in the liquid phase under reaction conditions. In those instances where the desired reaction conditions are insufficient to render the reactants liquid, or where diluents may be desired, inert solvents may be employed. Such solvents are well-known to the art and include such things as hydrocarbons (e.g., benzene, toluene and paraffins), ethers, chloroform and other inert materials capable of dissolving the organic reactants.
The higher alkyl arylsulfonate product produced by the alkyl exchange process of this invention is readily hydrolyzed to convert the high alkyl moieties to the corresponding higher alkanols which have a variety of known uses, e.g., solvents, precursors for detergents,
etc.
The following examples will serve to further illustrate the invention.
EXAMPLE 1 To a ml Erlenmyer flask there were charged 0.1 mol ethylbenzene sulfonate, 0.1 mol n-octyl bromide and about 0.5 g tributylhexadecylammonium bromide. The flask was fitted with a condenser and stirrer. With stirring, the reaction mixture was heated to about 60C and maintained for 12 hours whereupon a sample was withdrawn and analyzed by gas chromatography. Analysis indicated that substantially equimolar amounts of ethylbenzene sulfonate, n-octylbenzene sulfonate, n-
ery of the desired product which is in a liquid state. This technique is particularly applicable to the general process wherein the lower alkyl arylsulfonates employed as reactants results in relatively highly volatile lower alkyl halides in the product mixture- EXAMPLE 2 Similar results as obtained in Example 1 using the same procedure may be produced by reacting eicosyl chloride and methyl p-bromobenzene sulfonate in the presence of tetranonylammonium hydroxide.
EXAMPLE 3 V Following Example 2, 2-ethylhexyl chloride and propylchlorobenzene sulfonate may be reacted in the presence of triphenyldecylphosphonium chloride to produce similar results.
EXAMPLE 4 l-methylheptadecyl chloride and ethyl pmethylbenzene sulfonate may be reacted in the presence 'of triberizyldecylarsonium chloride as described I in 'E'xam plej'to effect alkyl'exchange.
EXAMPLE 5 Alkyl exchange may be effected similarly as described in 'Example 2 by reacting decyl bromide with methylbe'nzene sulfonate in the presence of trioctylethylammonium bromide.
Thus having described the invention in detail, it will be understood by those skilled in the art that certain variations and modifications may be made without departing from the spirit and scope of the invention as described herein and in the appended claims.
We claim:
' l. A process for exchanging alkyl moieties between 7 compounds which comprises reacting a lower alkyl aryl :sulfonate with a higher alkyl halide at temperatures in :thexrangc of 0C to 200C in the presence of at least 0.01 weight percent of an organic quaternary salt based on the total alkyl halide and alkyl aryl sulfonate; said lower alkyl aryl sulfonate being defined by-the formula Rlln wherein n is zero or one; R is halogen or C to C alkyl group, and R" is a C and C alkyl group; said higher alkyl halide being defined by the formula RX wherein R is. a straight or branch chain alkyl grup having 6 to 40 carbon atoms and X is chlorine, bromine, or iodine; said alkyl moieties being exchanged being R and R;
and said organic quaternary salt being defined by the formula (R1R2R3R4M X wherein M is a pentavalent ion of an element selected from the group consisting of nitrogen and phosphorus; each of R R R and R independently, is an alkyl group having 1 to 30 carbon atoms, a phenyl group, a benzyl group, or an alkyl substituted benzyl group wherein the alkyl group has 1 to 30 carbon atoms, and X is hydroxide, bromine, chlorine, iodine, sulfate, paratoluene sulfonate or acetate.
2. A process according to claim 1 wherein the organic quaternary salt is present in an amount in the range of 0.01 to 10 weight percent based on the alkyl halide and alkyl arylsulfonate.
3. A process according to claim 1 wherein the lower alkyl arylsulfonate is methyl para-methyl benzene sulfonate, methyl para-bromo benzene sulfonate, ethylbenzene sulfonate, butyl-benzene sulfonate, propylchloro-benzene sulfonate, ethyl para-methyl benzene sulfonate, or ethyl butylbenzene sulfonate.
4. A process according to claim 1 wherein X is bromine, chlorine, hydroxy or para-toluene sulfonate.
5. The process according to claim 1 wherein M is nitrogen.
6. The process according to claim 1 wherein M is phosphorus.
7. A process for exchanging alkyl moieties between compounds which comprises reacting a lower alkyl aryl sulfonate with a higher alkyl halide at temperatures in the range of 0C to 200C in the presence of an inert solvent and at least 0.01 weight percent of an organic quaternary salt based on the total alkyl halide and alkyl aryl sulfonate; said lower alkyl aryl sulfonate being defined by the formula wherein n is zero or one; R is halogen or C to C alkyl group, and R" is a C to C alkyl group; said higher alkyl halide being defined by the formula RX wherein R is a straight or branch chain alkyl group having 6 to 40 carbon atoms and X is chlorine, bromine, or iodine; said alkyl moieties being exchanged being R and R"; said inert solvent being benzene, toluene, paraffin, ether, or chloroform; and said organic quaternary salt being defined by the formula (R R R R M) X- wherein M is a pentavalent ion of an element selected from the group consisting of nitrogen and phosphorus; each of R R R and R independently, is an alkyl group having 1 to 30 carbon atoms, a phenyl group, a benzyl group, or an alkyl substituted benzyl group wherein the alkyl group has 1 to 30 carbon atoms, and X is hydroxide, bromine, chlorine, iodine, sulfate, paratoluene sulfonate or acetate.
* III =l=

Claims (7)

1. A PROCESS FOR EXCHANGING ALKYL MOIETIES BETWEEN CMPOUNDS WHICH COMPRISES REACTING A LOWER ALKYL ARYL SULFONATE WITH HIGHER ALKYL HALIDE AT TEMPERATURE IN THE RANGE OF 0*C TO 200$C IN THE PRESENCE OF AT LEAST 0.01 WEIGHT PERCENT OF AN ORGANIC QUATERNARY SALT BASED ON THE TOTAL ALKYL HALIDE AND ALKYL ARYL SULFONATE, SAID LOWER ALKYL ARYL SULFONATE BEING DEFNED BY THE FORMULA
2. A process according to claim 1 wherein the organic quaternary salt is present in an amount in the range of 0.01 to 10 weight percent based on the alkyl halide and alkyl arylsulfonate.
3. A process according to claim 1 wherein the lower alkyl arylsulfonate is methyl para-methyl benzene sulfonate, methyl para-bromo benzene sulfonate, ethyl-benzene sulfonate, butyl-benzene sulfonate, propyl-chloro-benzene sulfonate, ethyl para-methyl benzene sulfonate, or ethyl butylbenzene sulfonate.
4. A process according to claim 1 wherein X is bromine, chlorine, hydroxy or para-toluene sulfonate.
5. The process according to claim 1 wherein M is nitrogen.
6. The process according to claim 1 wherein M is phosphorus.
7. A process for exchanging alkyl moieties between compounds which comprises reacting a lower alkyl aryl sulfonate with a higher alkyl halide at temperatures in the range of 0*C to 200*C in the presence of an inert solvent and at least 0.01 weight percent of an organic quaternary salt based on the total alkyl halide and alkyl aryl sulfonate; said lower alkyl aryl sulfonate being defined by the formula
US371230A 1973-07-02 1973-07-02 Alkyl arylsulfonate exchange process Expired - Lifetime US3914272A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US371230A US3914272A (en) 1973-07-02 1973-07-02 Alkyl arylsulfonate exchange process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US371230A US3914272A (en) 1973-07-02 1973-07-02 Alkyl arylsulfonate exchange process

Publications (1)

Publication Number Publication Date
US3914272A true US3914272A (en) 1975-10-21

Family

ID=23463068

Family Applications (1)

Application Number Title Priority Date Filing Date
US371230A Expired - Lifetime US3914272A (en) 1973-07-02 1973-07-02 Alkyl arylsulfonate exchange process

Country Status (1)

Country Link
US (1) US3914272A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2297260A2 (en) * 1975-01-10 1976-08-06 Kernforschungsanlage Juelich PROCESS FOR THE PREPARATION OF SULPHONES
WO2002086034A1 (en) * 2001-04-20 2002-10-31 Exxonmobil Research And Engineering Company Servo valve erosion inhibited aircraft hydraulic fluids

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Hoffmann, J. Chem. Soc., 1965, pp. 6753-6769. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2297260A2 (en) * 1975-01-10 1976-08-06 Kernforschungsanlage Juelich PROCESS FOR THE PREPARATION OF SULPHONES
WO2002086034A1 (en) * 2001-04-20 2002-10-31 Exxonmobil Research And Engineering Company Servo valve erosion inhibited aircraft hydraulic fluids
US6599866B2 (en) 2001-04-20 2003-07-29 Exxonmobil Research And Engineering Company Servo valve erosion inhibited aircraft hydraulic fluids

Similar Documents

Publication Publication Date Title
Silvestru et al. Tetraorganodichalcogenoimidodiphosphorus acids and their main group metal derivatives
CA1154789A (en) Process for the preparation of vinylcyclopropane derivatives
US3914272A (en) Alkyl arylsulfonate exchange process
US3664966A (en) Dehydrohalogenation catalyst
US3325546A (en) Process for the preparation of detergent phosphine oxides
US2437798A (en) New secondary organic phosphorus halides and processes for making the same
US2520400A (en) Production of sulfenamides
US3389183A (en) Process for the preparation of tertiary phosphines
US4500471A (en) Preparation of trifluoromethyl-benzoyl halides
US3322822A (en) Preparation of halosulfonyl benzoyl halides
US3256351A (en) Conversion of o-nitrochlorobenzene to o-dichlorobenzene
US3121737A (en) Sulfonic acid formation via sulfonation of trialkyl and triarylalkyl aluminum
US3336391A (en) Synthesis of ketones and sulfones
US3799999A (en) Synthesis of primary alkyl halides
US3629346A (en) Reactions of alkali metal tetraalkylaluminum compounds with diatomic halogens
US2889377A (en) Chloroalkylation of aromatic compounds
US3468971A (en) Reactions of alkali metal tetraalkyl-aluminum compounds with active halogen compounds
US3780045A (en) Preparation of organolithium compounds
PT93329A (en) PROCESS FOR THE PREPARATION OF N-ALYMETATRIFLUOROMETHANTILINE
US3824295A (en) Preparation of ethers
US3793380A (en) Preparation of dihalo compounds
US3914327A (en) Catalyzed halogen exchange process
US3812212A (en) Process for increasing selectivity to 1-bromoalkane in the addition of hydrogen bromide to olefins
US5015775A (en) Alkyl aryl sulfones and method of preparing the same
US3697628A (en) Benzylation of triaryl phosphates