CA1086778A - Process for the manufacture of 1,1-dihalo-4-methyl-1, 3-pentadienes - Google Patents
Process for the manufacture of 1,1-dihalo-4-methyl-1, 3-pentadienesInfo
- Publication number
- CA1086778A CA1086778A CA289,709A CA289709A CA1086778A CA 1086778 A CA1086778 A CA 1086778A CA 289709 A CA289709 A CA 289709A CA 1086778 A CA1086778 A CA 1086778A
- Authority
- CA
- Canada
- Prior art keywords
- methylpentane
- tetrahalo
- chloride
- methyl
- reaction
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/19—Halogenated dienes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
Landscapes
- 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)
Abstract
Abstract of the Disclosure The dehydrohalogenation of a 1,1,1,3-tetrahalo-4-methylpentane to a 1,1-dihalo-4-methyl-1,3-pentadiene is accomplished in the liquid phase in the presence of a catalytic amount of stannic chloride. The diene is a useful intermediate in the manu-facture of insecticidal synthetic pyrethroid esters.
Description
~ 77 ~
Back~round o the Invention Synthetic pyrethroid esters, s~milar in structure to naturally occurring pyre~hrin, are well known as insectlcides of high stability and low mammalian toxicity. These synthetlc es~ers are superior to the pyrethrins found in nature in a number of waysO Firs~, the na~urally occurring pyrethrins are subject to very fas~ degradation and ~heir insectici~al activity is neu~alized by air and ligh~. Second7 the nat~lrally occurring compounds are not available in great abunda~ce and are costly to e~tract from their natural state. The syn~hesized variations 10 of these compounds, on the other hand~ have a higher stability9 and yet are suffic~ently degradable ~ha~ they do not present : environmental problems. They are also resistan~ ~o light induced oxidation. In addition, pyrethroids have a low toxicity for mammal~ and humans, rela~ive to o~her insecticide~, while . 15 exh~biting h~gh însect~cidal act~vi~y to a wide variety o~ insects.
. One of the methods of preparation of these synthetic pyrethroids i~ disclosed ln P,E. BlLrt, M. Elliott9 A.W. Farn~am, .F. Jane~, P.H. Needham, and D,A. Pullman, Pesticide Science 5, 791-799 (1974). According to this method, ethyldiazoacetat8 ~ reacted with 1,1-dichloro-4-methylpenta-1,3~diene to ~orm ethyl(~)-ci9, tran~-2,2-dimathyl-3-(2,2-dichlorov~nyl)-cyclo-propanecarboxylate, which is then converted to the carboxyl~c acld. The la~ter was subsequently converted to the acid chlor~de~
then reacted with 3-phenoxybenzyl alcohol ln a Schotten-Bauman~
reaction~ to produce 3-phenoxybenzyl 292-dimethyl-3-(2,2-.~ , .
: dichlorovi~yl)-cyclopropanecarboxylate, a well known insecticidally ~:
ac~ive:pyre~hroid ester. The above-mentioned diene can b~ prepared ' ' '':' , . , . , . . . - ................... .
-~ 6~
by the reaction of an appropriate sulfone with sodi~m hydroxide in a Ramberg-Backland type rearrangement. See L. R~mberg and B Backland, Ark;v. Kemi. Mineral. Geol., 13A, No. 27 (1940);
also Bordwell and Cooper, J, Am. Chem. Soc., 73, 5187-5190 (1951).
The process involves a large number of steps, including those for the preparation of the sulfone, and requires the use of costly reagents.
:
- The diene has also been prepared from chloral and isobutylene, Farlcas, Kourim, and Sorm, Collection Czechoslov.
Chem. Commun., 24, 2230-2236 (1959), in a four-step process involving a costly zinc elimination.
A simpler process involves the addition of carbon tetrachloride to 3-methyl-1-butene to form 1,1~1,3~tetrachloro- ;
4-methylpentane, followed by a liquid phase dehydrochlorination to form 1,1-dichloro-4-methyl-1,3-pentadiene. A variety of materials are known ~o catalyze ~his or similar liquid phase dehydrochlorinations 3 notably BF3 and FeC13, see Topchiev9 Bogomolova, and Gol'dfarb, Doklady Akad. Na~k S.S.S.R., 107, 420-3 (1956), and ~elgian Patent 621,439. These known catalytic processes.sufer from low yields due to polymerization of the product.
The object of this lnvention is to provide a novel process for the dehydrohalogenation of a 1,191,3-tetrahalo-4-methyl2entane which entails polymerization to much less an extent than kno~ processes, and thus produces higher yields of the desired product. ~i .. . . , ~ . .: . .. . . . .
~ 7 8 Brief Description of the Invention This inventioo relates to a process for the manufacture of 1,1-dihalo-4-methyl-1?3-pentadiene which com?rises contacting a 1,1,1~3-tetrahalo-4-methylpen~ane with a catalytic amount of stannic chloride, and recovering the product therefrom.
Detailed Description of the Invention In the process of the present invention~ liquid stannic chloride, SnC14, is used as a cracking catalyst in the following reaction: CH CH
1 3 SnC14 / 3 CX3-CH2-CHX-CH-CH3 --> CX2=CH-CH-~ + 2 ~ . .
where X is a halogen selected from the group consisting of chlorine, bromine, and fluorîne. The four X atoms in the molecule on the le~t hand side of the above equation may all be the same halogen, or may comprise a combination o two diferent halogens selected from the above group. A typical example of such a molecule combining two different halogens is l,l,l-trichloro-3-bromo-4-methylpen~ane. The result upon cracking this molecule lS is 1,1-dichloro-4-methyl-1,3-pentadiene plus one mole each of HCl and HBr. The preferred halogen, or reasons of utillty of the ~inal product~ is chlorineO Thus, the preferred reactant ln the above equation is 1~1,173-tetrachloro-4-methylpentane ~nother example of a reactant w~h ~wo different halogens is ~0 1~1-di~luoro-1,3-dibromo-4-methylpentane.
The term "catalytic amount" is used herein to denote an~ amount o stannic chloride which will enhance the ?rogress of the reaction. Reasonable reaction rates are normally achieved : .
-4~
~ 3~;'7~7~
when the stannic chloride concentration is between about 0.25%
and about 10.0% by weight wlth respect to the 1,1,1,3-tetrahalo-4-methylpentane. The preferred range is be~ween about 0.5%
and about 5 0% by weight.
- 5 Although the reaction temperature is not an essential aspect of the invention, the temperature chosen will be limited by practical considerations read~ly apparent to the skilled practitioner. Co~siderations of economy in terms o~ heat inpu~
- and overall reaction time will dictate the lower ~emperature limit, while the boiling points of the components will dictate the upper temperature limit. The latter can be varied by adjustments in the system pressure In particular, superatmos-pheric pressures will al~ow liquid phase operation at higher temperatures. The result will be an increased reaction rate.
In general, it will be most convenient to opera~e the reaction at a temperature between about 120C and about 200C, pref~ably between about 140~C and about 170C. Since both the initial compound~ the cat~lyst and the desired end product, are in the liquid phase, the reaction will proceed most effectively ~7hen the system is under reluxO The hydrogen halide by-product leaves the system as a gas, the evolution of which causes the volatili-zation and subsequent removal from the system of some of the catalyst, thus necessitating the use of a large initial quantity o catalyst in the reaction mixture. The amount sf cstalyst 2S lost in this manner can be reduced by operating the system at superatmospheric pressures3 for example, up to 25 psig. As mentioned above, the higher pressure will have the ~urther advan~age of inereasing the reaction rate of the reflux~ng system. . ~ ~
. ;'. ' .
' ;' :' ..
'~
.,. . ~ . ;. - , ~ .
77~
The presenc~ of air in the system will be detrimental to the purity of the final produc~, since air will ~orm perox1des with the resul~ing diene~ which will in turn lead to polymeriza-tion. During ~he cracking proces~, however, the evolution of the hydrogen halide gas serves to sw~ep ~he air out the sys~em, and thu~ prevent the ormation o:E the harmful peroxides. Af~er the crack~ng proce~s ~s comple~edg it will be advantageous to add a ~tab~lizer to the system to prevent polymerization. Thi~ purpose can be served by any of the known stabilizlng agents such 88 t-butyl catechol and Ionol~ (a~ an~ioxidant defined as a tri~
substituted phenol - product of Shell Chemical Company).
At the completion of the reaction, the product can be recovered ~rom the reaction mixture by any of the conventional liquid recovery techniques. Additionally, the stannic chloride~ ~-remaining in the system can be distilled off and retained for reuse. The most use~ul recovery techniques will be vacuum dis-~illat~on followed by steam distillation. The latter is particul rly useul for the separatlon of the desired diene from a~y polym~r :
formed dur~ng the reactio~.
' The advantage o~ the stannic chloride cat~lyst over ; other known catalysts i8 th~t it enhances the progre~s o the reaction with a minimum amount of polymerization. Yields on th~ order o 85 to 95% are readily obtainable wi~h stannic chlorlde but are lowered by polymerization of the product during or subsequent to the reaction. T~e yield will be ~he highest when polymer~zatio~ is suppre~sed in the manner indicated above.
~6-- :
~ , .
, . .
The 1,1,1,3-tetrahalo-4-methylpentane referred to in the reac~ion above can be prepared by any technique known in the art One method of preparation is the addition reaction of a te~rahalo methane to 3-methyl l-butene. Where the four halogens in the resulting substituted pentane are identical, the halogens in the tetrahalomethane are likewise identical and comprise the same four that exist in ~he product~ The preferred tetrahalo-methane is carbon tetrachloride. The addition reaction can also be run wi~h a tetrahalomethane which contains ~o different types of halogen. Examples of the latter are CC13~r and CF2Br2. In the former case, the resulting substituted pentane is 19l ,1-trichloro 3-bromo-4-methylpentane. In the latter l,l-dichloro-1,3-difluoro-4-methylpentane will result. Either of these substituted pentanes can be used in the cracking reaction described above. A variety of catalysts are known in the art for use in the above described addition reaction. Among these are cuprlc chloride 7 cuprous chloride, ferric chloride, ferrous - `
chloride, ferrous chloride with benzoin, ruthenium(~ triphenyl-phosphine complexes, organic peroxides, and cobal~ous salts.
Examples of ruthenium~ triphenylphosphine complexes are dichlorotris(triphenylphosphine)ruthenium(II) and dichlorotetra-lcis(triphenylphosphine)ruthenium(II).
.
The organic pero~id~ tincluding hydrogen peroxide~ are ..
defined by the ormula R-O-O-R' wherein R and R' are hydrogen or organic radicals. These include the hydroperoxides~ where R
is hydrogen and R' is alkyl, cycloalkyl, cycloalkenyl, alkaryl, aralkyl~ and heterocyclic of up to 12 carbon atoms; the dialkyl peroxides, w~ere R and R9 are each alkyl of up to 12 carboo atoms;
, . ~,. . . . . . . ~ . .
-the diaralkyl peroxides, where R and R' are each arallcyl of up to 20 carbon atoms; the aliphatic peroxy acids ~here R is hydrogen and R' is alkanoyL or aroyl of up to 12 carbon atoms; the peroxy esters o~ said pero~y acids, where R is alkyl or aryl of up to 12 carbon atoms and R' is alkanoyl or aroyl of up to 12 carbon a~oms; the diacyl peroxides, where R and R' each are alkanoyl of up to 12 carbon atoms; the diaroyl peroxides, where R and R' each are aroyl of up to 12 carbon a~oms as well as the dialkyl peroxy-dicarbonateg, l-hydroxyalkyL hydroperoxides, bis(l-hydroxyalkyl) peroxides, polyalkylidene peroxi~es, alkyl ~-hydroalkyl peroxides and peroxy acetals Preferred organic peroxides are those wherein ~ and R' are hydrogen, alkyl vf 1-4 carbon atoms, aralkyl of up to 12 carbon atoms, alkanoyl of up to 12 carbon atoms, or aroyl of up to 12 carbon atoms : Any cobaltous salt soluble in the tetrahalomethane used will be sui~able in the addition reaction. Such salts include cobaltous hexamine naphthalene ~ -sulfonate, cobaltous hexamine picrate, and the various cobaltous alkylated-naphthalene ~20 sul~onates, for example, cobaltous methyl naphthalenesulfonate and cobaltous ethyl naphthalenesulfonate.
.
The following examples are of~ered to illustrate the process of the invention, and are not intended to impose ~ -limitations thereon.
EXAMPL~ I
~5 A 12-ounce aerosol compatibility tube was charged with ` tha following:
.
:;
.
~ 6~7 175 ml (1.75 moles) CCl~
0.2002 g dichlo~o~ris(triphenyl-phosphine)ruthenium(II) 105 g (l.S moles) 3-methylbutene The air in the tube was displaced and the tube was placed in a bath at 75C for 20 hours with sti ring. The tube and contents were then cooled3 and the unreacted CC14 and 3-methylbutene were removed by distillation~ leaving 286 g (85% yield) of 1,1,~,3-tetrachloro-4-methylpentane, with 96% purity.
A stirred reaction flask with reflux condenser was . .
charged with 508 g (4.00 ml, about 2.3 moles) o~ 1,1,1,3-tetra-chloro-4-methylpentane prepared by the above procedure, and 10 ml of SnC14. The system was heated to reflux ~or four hours. 0 :~.
the starting material~ 5/0 remained uncracked. Steam distillation of the product yielded 310 g (88% yield) of 1,1-dichloro-4-methyl-.
1, 3-pentadiene, with an assay by chromatography of 97%.
' . ': ' .
EXAMPLE II
A 2-liter reactor was charged with 1288 g (1 lîter, 5.75 moles) of 1,1,1~3-tetrachloro-4-methylpentane, prepared ~n ~. .
a manner s~m~lar to that descr;bed in Example I, and 25 ml SnC14. .
The system was re1uxed at 170C. During reflux, gas chr~ma~o 20 graphy analyses provided the follo~;Lng data: :
Reaction Time % Cracked - , I 1 1/4 hours 29 ~ ~ ,. . .
3 1/4 hours 65 5 114 hours 85.5 .6 1/4 hours go , '' ' ' .. .. . . . . . . .. . .. . . . . . . ~. . . .... ~ .. :. .. . .. . . . . . .
~ ;'7~ ~
The produc~ was vacuum distilled to yield 758 g of the diene in the distilLate. To ~he residue was added 150 ml con-centrated HCl diluted ~7ith ~7ater to 400 ml. The residue was then s~eam distilled to yield an additional 61 g of the diene, to make a total o~ 819 g (94% yield), identity confirmed by gas chromatographic analysis.
EXAIV~LE III
This example illustrates ~he results achieved when ferric chloride rather than stannic chloride is used as the cracking catalyst. The advantages of the stannic chlorid~ pro-cess are apparent from the data below.
A 500 ml reactor equipped with stirrer and condenser was charged with 200 ml (256 g, 1.14 moles) of 1,1,1,3-tetrachloro-4-methyl-pentane, and 10 g of FeC13. The mixture was heated to reflux at about 160C. After about 1 hour, the reaction mixture formed a thick gel. A solution of 40 ml concentrated HCl diluted to 100 ml with dis~illed water was added to the gel9 snd the mixture was steam distilled. Of a possible 170 g (theoretical amount), onLy llL g of unpolymeriæed material was recovered. Of this amount, 47.5% was the uncracked starting material, and 34.4~O was the desired produc~. Conversion was 66~/o~ with a yield of 35%.
10~
.
: .. . . . .. . . - . .
Back~round o the Invention Synthetic pyrethroid esters, s~milar in structure to naturally occurring pyre~hrin, are well known as insectlcides of high stability and low mammalian toxicity. These synthetlc es~ers are superior to the pyrethrins found in nature in a number of waysO Firs~, the na~urally occurring pyrethrins are subject to very fas~ degradation and ~heir insectici~al activity is neu~alized by air and ligh~. Second7 the nat~lrally occurring compounds are not available in great abunda~ce and are costly to e~tract from their natural state. The syn~hesized variations 10 of these compounds, on the other hand~ have a higher stability9 and yet are suffic~ently degradable ~ha~ they do not present : environmental problems. They are also resistan~ ~o light induced oxidation. In addition, pyrethroids have a low toxicity for mammal~ and humans, rela~ive to o~her insecticide~, while . 15 exh~biting h~gh însect~cidal act~vi~y to a wide variety o~ insects.
. One of the methods of preparation of these synthetic pyrethroids i~ disclosed ln P,E. BlLrt, M. Elliott9 A.W. Farn~am, .F. Jane~, P.H. Needham, and D,A. Pullman, Pesticide Science 5, 791-799 (1974). According to this method, ethyldiazoacetat8 ~ reacted with 1,1-dichloro-4-methylpenta-1,3~diene to ~orm ethyl(~)-ci9, tran~-2,2-dimathyl-3-(2,2-dichlorov~nyl)-cyclo-propanecarboxylate, which is then converted to the carboxyl~c acld. The la~ter was subsequently converted to the acid chlor~de~
then reacted with 3-phenoxybenzyl alcohol ln a Schotten-Bauman~
reaction~ to produce 3-phenoxybenzyl 292-dimethyl-3-(2,2-.~ , .
: dichlorovi~yl)-cyclopropanecarboxylate, a well known insecticidally ~:
ac~ive:pyre~hroid ester. The above-mentioned diene can b~ prepared ' ' '':' , . , . , . . . - ................... .
-~ 6~
by the reaction of an appropriate sulfone with sodi~m hydroxide in a Ramberg-Backland type rearrangement. See L. R~mberg and B Backland, Ark;v. Kemi. Mineral. Geol., 13A, No. 27 (1940);
also Bordwell and Cooper, J, Am. Chem. Soc., 73, 5187-5190 (1951).
The process involves a large number of steps, including those for the preparation of the sulfone, and requires the use of costly reagents.
:
- The diene has also been prepared from chloral and isobutylene, Farlcas, Kourim, and Sorm, Collection Czechoslov.
Chem. Commun., 24, 2230-2236 (1959), in a four-step process involving a costly zinc elimination.
A simpler process involves the addition of carbon tetrachloride to 3-methyl-1-butene to form 1,1~1,3~tetrachloro- ;
4-methylpentane, followed by a liquid phase dehydrochlorination to form 1,1-dichloro-4-methyl-1,3-pentadiene. A variety of materials are known ~o catalyze ~his or similar liquid phase dehydrochlorinations 3 notably BF3 and FeC13, see Topchiev9 Bogomolova, and Gol'dfarb, Doklady Akad. Na~k S.S.S.R., 107, 420-3 (1956), and ~elgian Patent 621,439. These known catalytic processes.sufer from low yields due to polymerization of the product.
The object of this lnvention is to provide a novel process for the dehydrohalogenation of a 1,191,3-tetrahalo-4-methyl2entane which entails polymerization to much less an extent than kno~ processes, and thus produces higher yields of the desired product. ~i .. . . , ~ . .: . .. . . . .
~ 7 8 Brief Description of the Invention This inventioo relates to a process for the manufacture of 1,1-dihalo-4-methyl-1?3-pentadiene which com?rises contacting a 1,1,1~3-tetrahalo-4-methylpen~ane with a catalytic amount of stannic chloride, and recovering the product therefrom.
Detailed Description of the Invention In the process of the present invention~ liquid stannic chloride, SnC14, is used as a cracking catalyst in the following reaction: CH CH
1 3 SnC14 / 3 CX3-CH2-CHX-CH-CH3 --> CX2=CH-CH-~ + 2 ~ . .
where X is a halogen selected from the group consisting of chlorine, bromine, and fluorîne. The four X atoms in the molecule on the le~t hand side of the above equation may all be the same halogen, or may comprise a combination o two diferent halogens selected from the above group. A typical example of such a molecule combining two different halogens is l,l,l-trichloro-3-bromo-4-methylpen~ane. The result upon cracking this molecule lS is 1,1-dichloro-4-methyl-1,3-pentadiene plus one mole each of HCl and HBr. The preferred halogen, or reasons of utillty of the ~inal product~ is chlorineO Thus, the preferred reactant ln the above equation is 1~1,173-tetrachloro-4-methylpentane ~nother example of a reactant w~h ~wo different halogens is ~0 1~1-di~luoro-1,3-dibromo-4-methylpentane.
The term "catalytic amount" is used herein to denote an~ amount o stannic chloride which will enhance the ?rogress of the reaction. Reasonable reaction rates are normally achieved : .
-4~
~ 3~;'7~7~
when the stannic chloride concentration is between about 0.25%
and about 10.0% by weight wlth respect to the 1,1,1,3-tetrahalo-4-methylpentane. The preferred range is be~ween about 0.5%
and about 5 0% by weight.
- 5 Although the reaction temperature is not an essential aspect of the invention, the temperature chosen will be limited by practical considerations read~ly apparent to the skilled practitioner. Co~siderations of economy in terms o~ heat inpu~
- and overall reaction time will dictate the lower ~emperature limit, while the boiling points of the components will dictate the upper temperature limit. The latter can be varied by adjustments in the system pressure In particular, superatmos-pheric pressures will al~ow liquid phase operation at higher temperatures. The result will be an increased reaction rate.
In general, it will be most convenient to opera~e the reaction at a temperature between about 120C and about 200C, pref~ably between about 140~C and about 170C. Since both the initial compound~ the cat~lyst and the desired end product, are in the liquid phase, the reaction will proceed most effectively ~7hen the system is under reluxO The hydrogen halide by-product leaves the system as a gas, the evolution of which causes the volatili-zation and subsequent removal from the system of some of the catalyst, thus necessitating the use of a large initial quantity o catalyst in the reaction mixture. The amount sf cstalyst 2S lost in this manner can be reduced by operating the system at superatmospheric pressures3 for example, up to 25 psig. As mentioned above, the higher pressure will have the ~urther advan~age of inereasing the reaction rate of the reflux~ng system. . ~ ~
. ;'. ' .
' ;' :' ..
'~
.,. . ~ . ;. - , ~ .
77~
The presenc~ of air in the system will be detrimental to the purity of the final produc~, since air will ~orm perox1des with the resul~ing diene~ which will in turn lead to polymeriza-tion. During ~he cracking proces~, however, the evolution of the hydrogen halide gas serves to sw~ep ~he air out the sys~em, and thu~ prevent the ormation o:E the harmful peroxides. Af~er the crack~ng proce~s ~s comple~edg it will be advantageous to add a ~tab~lizer to the system to prevent polymerization. Thi~ purpose can be served by any of the known stabilizlng agents such 88 t-butyl catechol and Ionol~ (a~ an~ioxidant defined as a tri~
substituted phenol - product of Shell Chemical Company).
At the completion of the reaction, the product can be recovered ~rom the reaction mixture by any of the conventional liquid recovery techniques. Additionally, the stannic chloride~ ~-remaining in the system can be distilled off and retained for reuse. The most use~ul recovery techniques will be vacuum dis-~illat~on followed by steam distillation. The latter is particul rly useul for the separatlon of the desired diene from a~y polym~r :
formed dur~ng the reactio~.
' The advantage o~ the stannic chloride cat~lyst over ; other known catalysts i8 th~t it enhances the progre~s o the reaction with a minimum amount of polymerization. Yields on th~ order o 85 to 95% are readily obtainable wi~h stannic chlorlde but are lowered by polymerization of the product during or subsequent to the reaction. T~e yield will be ~he highest when polymer~zatio~ is suppre~sed in the manner indicated above.
~6-- :
~ , .
, . .
The 1,1,1,3-tetrahalo-4-methylpentane referred to in the reac~ion above can be prepared by any technique known in the art One method of preparation is the addition reaction of a te~rahalo methane to 3-methyl l-butene. Where the four halogens in the resulting substituted pentane are identical, the halogens in the tetrahalomethane are likewise identical and comprise the same four that exist in ~he product~ The preferred tetrahalo-methane is carbon tetrachloride. The addition reaction can also be run wi~h a tetrahalomethane which contains ~o different types of halogen. Examples of the latter are CC13~r and CF2Br2. In the former case, the resulting substituted pentane is 19l ,1-trichloro 3-bromo-4-methylpentane. In the latter l,l-dichloro-1,3-difluoro-4-methylpentane will result. Either of these substituted pentanes can be used in the cracking reaction described above. A variety of catalysts are known in the art for use in the above described addition reaction. Among these are cuprlc chloride 7 cuprous chloride, ferric chloride, ferrous - `
chloride, ferrous chloride with benzoin, ruthenium(~ triphenyl-phosphine complexes, organic peroxides, and cobal~ous salts.
Examples of ruthenium~ triphenylphosphine complexes are dichlorotris(triphenylphosphine)ruthenium(II) and dichlorotetra-lcis(triphenylphosphine)ruthenium(II).
.
The organic pero~id~ tincluding hydrogen peroxide~ are ..
defined by the ormula R-O-O-R' wherein R and R' are hydrogen or organic radicals. These include the hydroperoxides~ where R
is hydrogen and R' is alkyl, cycloalkyl, cycloalkenyl, alkaryl, aralkyl~ and heterocyclic of up to 12 carbon atoms; the dialkyl peroxides, w~ere R and R9 are each alkyl of up to 12 carboo atoms;
, . ~,. . . . . . . ~ . .
-the diaralkyl peroxides, where R and R' are each arallcyl of up to 20 carbon atoms; the aliphatic peroxy acids ~here R is hydrogen and R' is alkanoyL or aroyl of up to 12 carbon atoms; the peroxy esters o~ said pero~y acids, where R is alkyl or aryl of up to 12 carbon atoms and R' is alkanoyl or aroyl of up to 12 carbon a~oms; the diacyl peroxides, where R and R' each are alkanoyl of up to 12 carbon atoms; the diaroyl peroxides, where R and R' each are aroyl of up to 12 carbon a~oms as well as the dialkyl peroxy-dicarbonateg, l-hydroxyalkyL hydroperoxides, bis(l-hydroxyalkyl) peroxides, polyalkylidene peroxi~es, alkyl ~-hydroalkyl peroxides and peroxy acetals Preferred organic peroxides are those wherein ~ and R' are hydrogen, alkyl vf 1-4 carbon atoms, aralkyl of up to 12 carbon atoms, alkanoyl of up to 12 carbon atoms, or aroyl of up to 12 carbon atoms : Any cobaltous salt soluble in the tetrahalomethane used will be sui~able in the addition reaction. Such salts include cobaltous hexamine naphthalene ~ -sulfonate, cobaltous hexamine picrate, and the various cobaltous alkylated-naphthalene ~20 sul~onates, for example, cobaltous methyl naphthalenesulfonate and cobaltous ethyl naphthalenesulfonate.
.
The following examples are of~ered to illustrate the process of the invention, and are not intended to impose ~ -limitations thereon.
EXAMPL~ I
~5 A 12-ounce aerosol compatibility tube was charged with ` tha following:
.
:;
.
~ 6~7 175 ml (1.75 moles) CCl~
0.2002 g dichlo~o~ris(triphenyl-phosphine)ruthenium(II) 105 g (l.S moles) 3-methylbutene The air in the tube was displaced and the tube was placed in a bath at 75C for 20 hours with sti ring. The tube and contents were then cooled3 and the unreacted CC14 and 3-methylbutene were removed by distillation~ leaving 286 g (85% yield) of 1,1,~,3-tetrachloro-4-methylpentane, with 96% purity.
A stirred reaction flask with reflux condenser was . .
charged with 508 g (4.00 ml, about 2.3 moles) o~ 1,1,1,3-tetra-chloro-4-methylpentane prepared by the above procedure, and 10 ml of SnC14. The system was heated to reflux ~or four hours. 0 :~.
the starting material~ 5/0 remained uncracked. Steam distillation of the product yielded 310 g (88% yield) of 1,1-dichloro-4-methyl-.
1, 3-pentadiene, with an assay by chromatography of 97%.
' . ': ' .
EXAMPLE II
A 2-liter reactor was charged with 1288 g (1 lîter, 5.75 moles) of 1,1,1~3-tetrachloro-4-methylpentane, prepared ~n ~. .
a manner s~m~lar to that descr;bed in Example I, and 25 ml SnC14. .
The system was re1uxed at 170C. During reflux, gas chr~ma~o 20 graphy analyses provided the follo~;Lng data: :
Reaction Time % Cracked - , I 1 1/4 hours 29 ~ ~ ,. . .
3 1/4 hours 65 5 114 hours 85.5 .6 1/4 hours go , '' ' ' .. .. . . . . . . .. . .. . . . . . . ~. . . .... ~ .. :. .. . .. . . . . . .
~ ;'7~ ~
The produc~ was vacuum distilled to yield 758 g of the diene in the distilLate. To ~he residue was added 150 ml con-centrated HCl diluted ~7ith ~7ater to 400 ml. The residue was then s~eam distilled to yield an additional 61 g of the diene, to make a total o~ 819 g (94% yield), identity confirmed by gas chromatographic analysis.
EXAIV~LE III
This example illustrates ~he results achieved when ferric chloride rather than stannic chloride is used as the cracking catalyst. The advantages of the stannic chlorid~ pro-cess are apparent from the data below.
A 500 ml reactor equipped with stirrer and condenser was charged with 200 ml (256 g, 1.14 moles) of 1,1,1,3-tetrachloro-4-methyl-pentane, and 10 g of FeC13. The mixture was heated to reflux at about 160C. After about 1 hour, the reaction mixture formed a thick gel. A solution of 40 ml concentrated HCl diluted to 100 ml with dis~illed water was added to the gel9 snd the mixture was steam distilled. Of a possible 170 g (theoretical amount), onLy llL g of unpolymeriæed material was recovered. Of this amount, 47.5% was the uncracked starting material, and 34.4~O was the desired produc~. Conversion was 66~/o~ with a yield of 35%.
10~
.
: .. . . . .. . . - . .
Claims (10)
1. A process for the manufacture of a 1,1-dihalo-4-methyl-1,3-pentadiene which comprises contacting a 1,1,1,3-tetrahalo-4-methylpentane with a catalytic amount of stannic chloride, and recovering the product therefrom.
2. The process of Claim 1 in which the system tempera-ture is between about 120°C and about 200°C.
3. The process of Claim 1 in which the system tempera-ture is between about 140°C and about 170°C.
4. The process of Claim 1 in which the process occurs while the system is under reflux.
5. The process of Claim 1 in which the amount of stannic chloride is between about 0.25% and about 10% by weight with respect to the 1,1,1,3-tetrahalo-4-methylpentane.
6. The process of Claim 5 in which the amount of stannic chloride is between about 0.5% and about 5% by weight with respect to the 1,1,1,3-tetrahalo-4-methylpentane.
7. The process of Claim 1 in which the 1,1,1,3-tetrahalo-4-methylpentane is 1,1,1,3-tetrachloro-4-methylpentane.
8. The process of Claim 1 in which the system is under reflux, the 1,1,1,3-tetrahalo-4-methylpentane is 1,1.1,3-tetrachloro-4-methylpentane, and the amount of stannic chloride is between about 0.5% and about 5% by weight with respect to the 1,1,1,3-tetrachloro-4-methylpentane.
9. The process of Claim 1 in which the 1,1,1,3-tetrahalo-4-methylpentane is prepared by the addition of a tetrahalomethane to 3-methyl-1-butene in the presence of a catalytic amount of a catalyst selected from the group consisting of metallic iron, cupric chloride, cuprous chloride, ferric chloride, ferrous chloride, ferrous chloride with benzoin, ruthenium(II)-triphenylphosphine complexes, organic peroxides and cobaltous salts.
10. The process of Claim 9 in which the tetrahalo-methane is carbon tetrachloride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US74280176A | 1976-11-18 | 1976-11-18 | |
| US742,801 | 1976-11-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1086778A true CA1086778A (en) | 1980-09-30 |
Family
ID=24986278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA289,709A Expired CA1086778A (en) | 1976-11-18 | 1977-10-27 | Process for the manufacture of 1,1-dihalo-4-methyl-1, 3-pentadienes |
Country Status (20)
| Country | Link |
|---|---|
| JP (1) | JPS5365805A (en) |
| AU (1) | AU510041B2 (en) |
| BE (1) | BE860826A (en) |
| BR (1) | BR7707664A (en) |
| CA (1) | CA1086778A (en) |
| CS (1) | CS193596B2 (en) |
| DD (2) | DD134640A5 (en) |
| DE (1) | DE2751435A1 (en) |
| DK (1) | DK508377A (en) |
| ES (1) | ES464267A1 (en) |
| FR (1) | FR2371402A1 (en) |
| GB (1) | GB1540198A (en) |
| HU (1) | HU175532B (en) |
| IL (1) | IL53408A (en) |
| IN (1) | IN146116B (en) |
| NL (1) | NL7712680A (en) |
| PL (1) | PL106098B1 (en) |
| RO (1) | RO76301A (en) |
| SU (1) | SU843731A3 (en) |
| ZA (1) | ZA776871B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3511153A1 (en) * | 1985-03-27 | 1986-10-02 | Wacker-Chemie GmbH, 8000 München | METHOD FOR PRODUCING CONNECTIONS WITH ALKYL RESIDUE MULTIPLE BY CHLORINE SUBSTITUTED |
| US8586804B2 (en) * | 2010-12-01 | 2013-11-19 | E. I. Du Pont De Nemours And Company | Synthesis of 1,1,3-trichloro-1-propene |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2410541A (en) * | 1942-04-10 | 1946-11-05 | Du Pont | Polyhalogenated olefins |
| NL70108C (en) * | 1949-12-30 | |||
| US3299152A (en) * | 1961-11-06 | 1967-01-17 | Toyo Koatsu Ind Inc | Preparation of alpha, omegadichloroolefin |
| GB1536685A (en) * | 1975-06-02 | 1978-12-20 | Shell Int Research | Process for the preparation of 1,1-dihalo-1,3-dienes |
-
1977
- 1977-10-27 CA CA289,709A patent/CA1086778A/en not_active Expired
- 1977-11-12 JP JP13525377A patent/JPS5365805A/en active Pending
- 1977-11-14 CS CS777459A patent/CS193596B2/en unknown
- 1977-11-15 RO RO7792125A patent/RO76301A/en unknown
- 1977-11-16 HU HU77SA3072A patent/HU175532B/en unknown
- 1977-11-16 GB GB47657/77A patent/GB1540198A/en not_active Expired
- 1977-11-16 DD DD77202110A patent/DD134640A5/en unknown
- 1977-11-16 DD DD77212565A patent/DD143424A5/en unknown
- 1977-11-16 FR FR7734439A patent/FR2371402A1/en not_active Withdrawn
- 1977-11-16 IL IL53408A patent/IL53408A/en unknown
- 1977-11-16 DK DK508377A patent/DK508377A/en not_active Application Discontinuation
- 1977-11-16 BE BE2056427A patent/BE860826A/en unknown
- 1977-11-17 BR BR7707664A patent/BR7707664A/en unknown
- 1977-11-17 ZA ZA00776871A patent/ZA776871B/en unknown
- 1977-11-17 NL NL7712680A patent/NL7712680A/en not_active Application Discontinuation
- 1977-11-17 AU AU30734/77A patent/AU510041B2/en not_active Expired
- 1977-11-17 DE DE19772751435 patent/DE2751435A1/en not_active Withdrawn
- 1977-11-17 IN IN1619/CAL/77A patent/IN146116B/en unknown
- 1977-11-18 SU SU772544102A patent/SU843731A3/en active
- 1977-11-18 ES ES464267A patent/ES464267A1/en not_active Expired
- 1977-11-18 PL PL1977202246A patent/PL106098B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2751435A1 (en) | 1978-05-24 |
| AU510041B2 (en) | 1980-06-05 |
| PL202246A1 (en) | 1978-07-31 |
| GB1540198A (en) | 1979-02-07 |
| BR7707664A (en) | 1978-06-13 |
| CS193596B2 (en) | 1979-10-31 |
| SU843731A3 (en) | 1981-06-30 |
| ES464267A1 (en) | 1978-08-01 |
| JPS5365805A (en) | 1978-06-12 |
| IL53408A (en) | 1981-02-27 |
| IL53408A0 (en) | 1978-01-31 |
| PL106098B1 (en) | 1979-11-30 |
| DD143424A5 (en) | 1980-08-20 |
| BE860826A (en) | 1978-05-16 |
| DK508377A (en) | 1978-05-19 |
| HU175532B (en) | 1980-08-28 |
| NL7712680A (en) | 1978-05-22 |
| FR2371402A1 (en) | 1978-06-16 |
| ZA776871B (en) | 1978-09-27 |
| RO76301A (en) | 1981-11-04 |
| AU3073477A (en) | 1979-05-24 |
| IN146116B (en) | 1979-02-24 |
| DD134640A5 (en) | 1979-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU688925B2 (en) | Process for the manufacture of 1,1,1,3,3-pentafluoropropane | |
| EP1430011B1 (en) | Process for producing fluoroolefins | |
| CA2015247C (en) | Process for preparing fluoroalkyl vinyl compound | |
| CA1086778A (en) | Process for the manufacture of 1,1-dihalo-4-methyl-1, 3-pentadienes | |
| England | Catalytic conversion of fluoroalkyl alkyl ethers to carbonyl compounds | |
| CA1293739C (en) | Process for preparing 2,2,3-trifluoropropionyl fluoride | |
| US3657306A (en) | Polyfluoroisoalkoxyalkyl isocyanates | |
| EP0877724B1 (en) | Process for making dihalodifluoromethanes and their homologues | |
| EP0199646B1 (en) | Process for preparing 6-alkoxy-5-trifluoromethyl-1-naphtoic acids and novel 1-cyano-naphtalene intermediates | |
| WO1998058892A2 (en) | Preparation of fluoroalkyl compounds and their derivatives | |
| US4271325A (en) | Process for the manufacture of 1,1-dihalo-4-methyl-1,3-pentadienes | |
| US6300532B1 (en) | Process for addition of haloalkanes to alkenes catalyzed by an organophosphite compound | |
| JP4684401B2 (en) | Method for producing perfluoroalkadiene | |
| US4740627A (en) | Synthesis of E,Z-11-tetradecen-1-al | |
| JPH0261447B2 (en) | ||
| US4968852A (en) | Trifluoromethylbenzoyl bromide and conversion of same to bromobenzotrifluoride | |
| Petrov | New Electrophilic Reaction of Perfluoroalkylethylenes. Synthesis and Some Reactions of 1-Halo-1, 1, 2-trihydroperfluoroalkenes-2 | |
| US5258547A (en) | Process for preparing halogenated compounds | |
| US5220082A (en) | Process for production of polyfluoroolefins | |
| US4411843A (en) | Conversion of 1,1,1-trichloroperhaloalkanes into perhaloalkanoyl chlorides | |
| EP0085095A4 (en) | Intermediates and process for insecticidal synthetic pyrethroids. | |
| EP0002077B1 (en) | Esters of substituted cyclopropanecarboxylic acids and process for the preparation thereof | |
| EP0312804A1 (en) | Synthesis of cis-9-tricosene | |
| CA1310018C (en) | Process for cleaving aliphatic ether compounds | |
| KR810000480B1 (en) | Process for the manufacture of 1,1-dihalo-4-methyl-1,3-pentadienes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |