WO2000034216A1 - Process for preparing trichloroalkane derivatives - Google Patents

Process for preparing trichloroalkane derivatives Download PDF

Info

Publication number
WO2000034216A1
WO2000034216A1 PCT/GB1999/003942 GB9903942W WO0034216A1 WO 2000034216 A1 WO2000034216 A1 WO 2000034216A1 GB 9903942 W GB9903942 W GB 9903942W WO 0034216 A1 WO0034216 A1 WO 0034216A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
process according
hydrogen
alkenyl
trichloroalkane
Prior art date
Application number
PCT/GB1999/003942
Other languages
French (fr)
Inventor
Jenny Marie Barks
David Anthony Jackson
Original Assignee
Syngenta Limited
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 Syngenta Limited filed Critical Syngenta Limited
Priority to EP99956225A priority Critical patent/EP1137618A1/en
Priority to AU12868/00A priority patent/AU1286800A/en
Priority to JP2000586666A priority patent/JP2002531537A/en
Priority to KR1020017007013A priority patent/KR20010101129A/en
Priority to IL14330699A priority patent/IL143306A0/en
Publication of WO2000034216A1 publication Critical patent/WO2000034216A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • 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

Definitions

  • the present invention relates to a process for preparing trichloroalkane derivatives by the photochemically initiated addition of chloroform to an alkene derivative.
  • the process is of particular use for the production of 4,4,4-trichlorobutane derivatives which are important intermediates and products in the chemical industry.
  • 4,4,4-trichlorobutane derivatives are useful as intermediates in the manufacture of pesticidal compounds of the type described in, for example, WO 95/24403.
  • 4,4,4-Trichlorobutane derivatives may also be used as intermediates in the manufacture of compounds having useful solvent properties.
  • a process for the production of a trichloroalkane derivative comprising reacting an alkene derivative with chloroform, characterised in that the process is initiated by photochemical cleavage of an initiator of formula (I):
  • Z is chloro or fluoro
  • X is hydrogen, C, ⁇ alkyl, C,_ 6 haloalkyl, -O-O-C(O)-Y or -O-O-Y
  • Y is hydrogen, C w alkyl or C ⁇ haloalkyl.
  • Alkyl is straight or branched chain and is, for example, methyl, ethyl, w-propyl, w-butyl, H-pentyl, w-hexyl, .sO-propyl, /7-butyl, sec-butyl, wo-butyl, tert-butyl or «e ⁇ -pentyl.
  • Haloalkyl groups are alkyl groups which are optionally substituted with one or more of the same or different halogen atoms. Halogen is fluorine, chlorine, bromine or iodine.
  • the process of the invention may provide higher yields of the trichloroalkane derivative and fewer by-products than corresponding processes, for example, those using thermal initiation, or photochemical processes performed in the absence of an initiator or with an initiator not having a trihalocarbonyl group.
  • the three Z groups in the initiator of formula (I) may be the same or different.
  • CZ 3 may be, for example, CF 2 C1, however CZ 3 is preferably CC1 3 .
  • X is preferably C w haloalkyl or -O-O-Y, wherein Y is C w haloalkyl.
  • Haloalkyl is preferably CF 2 C1, more preferably CC1 3 .
  • Preferred examples of initiators of formula (I) include 1,3-dichloro-l, 1,3,3- tetrafluoroacetone, chloral and, especially, hexachloroacetone.
  • the alkene derivative used in the process of the invention preferably has a terminal double bond.
  • the process of the invention is of particular use for the production of 4,4,4-trichlorobutane derivatives, as illustrated in Scheme I below, wherein Z and X are as described above for formula (I);
  • W is C, ⁇ alkyl, C w alkenyl, OR 1 or NR 2 R 3 ;
  • R 1 is hydrogen, C, ⁇ alkyl, C 2 . 6 alkenyl, C 6 . l0 aryl or R 4 C(O);
  • R 2 and R 3 are, independently, hydrogen, C,. 6 alkyl, C ⁇ alkenyl or C 6 . 10 aryl; and
  • R 4 is C,. 6 alkyl, C 2.6 alkenyl, C 6.I0 aryl, C, ⁇ alkyloxy, C 2 . 6 alkenyloxy or C 6 . I0 aryloxy.
  • Alkenyl moieties may be in the form of straight or branched chains and, where appropriate, may be of either (E)- or (Z)-conf ⁇ guration. Examples include vinyl and allyl.
  • Aryl is phenyl or naphthyl. Therefore, in a preferred aspect of the invention the alkene derivative is a compound of formula (II):
  • W is C ⁇ alkyl, C 2 . 6 alkenyl, OR 1 or NR 2 R 3 ;
  • R 1 is hydrogen, C,. 6 alkyl, C 2.6 alkenyl, C 6 ., 0 aryl or R C(O);
  • R 2 and R 3 are, independently, hydrogen, C,. 6 alkyl, C 2 ⁇ alkenyl or C 6.
  • R 4 is C,. 6 alkyl, C 2 . 6 alkenyl, C 6 . 10 aryl, C, ⁇ alkyloxy, C 2.6 alkenyloxy or C 6 ., 0 aryloxy.
  • Initiation of the process of the invention is preferably achieved by irradiating the reaction mixture with light of a wavelength of from about 200 to about 600nm, more preferably 200 to 350nm, for example a wavelength of 254nm.
  • the light may be supplied by a low, medium or high pressure mercury lamp.
  • the reaction is preferably conducted at a temperature of about 0 to about 150°C and a temperature of from 25 to 150°C (such as 25 to 70°C) is particularly preferred.
  • the period of the reaction may be from about 30minutes to about 24hours, depending upon the volume of reactants and the temperature used. Generally a period of from about lhour to 12hours is sufficient.
  • EXAMPLE 1 This Example illustrates various preparations of 4,4,4-trichlorobutanol and the tabulated results show the increased 'yield on conversion' obtained when using the process of the invention compared to the corresponding process in the absence of an initiator.
  • the general procedure used in each case was the same: Chloroform was degassed for lhour with nitrogen immediately prior to use. A photochemical cell fitted with a condenser was charged with chloroform, allyl alcohol and (where appropriate) an initiator. The reaction mass was then degassed with nitrogen for a further 15minutes. The vessel was covered in aluminium foil and a uv screen was fitted. The reaction mixture was heated to the stated temperature using an oil bath, whereupon irradiation was carried out for the stated period of time, using light of the stated wavelength. Analysis of the reaction mixture was carried out by GC analysis.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

According to the present invention there is provided a process for the production of a trichloroalkane derivative comprising reacting an alkene derivative with chloroform, characterised in that the process is initiated by photochemical cleavage of an initiator of formula (I), wherein Z is chloro or fluoro; X is hydrogen, C1-6 alkyl, C1-6 haloalkyl, -O-O-C(O)-Y or -O-O-Y; and Y is hydrogen, C1-6 alkyl or C1-6 haloalkyl. The process is of particular use for the production of 4,4,4-trichlorobutane derivatives.

Description

PROCESS FOR PREPARING TRICHLOROALKANE DERIVATIVES The present invention relates to a process for preparing trichloroalkane derivatives by the photochemically initiated addition of chloroform to an alkene derivative. The process is of particular use for the production of 4,4,4-trichlorobutane derivatives which are important intermediates and products in the chemical industry. As an example, 4,4,4-trichlorobutane derivatives are useful as intermediates in the manufacture of pesticidal compounds of the type described in, for example, WO 95/24403. 4,4,4-Trichlorobutane derivatives may also be used as intermediates in the manufacture of compounds having useful solvent properties. According to the present invention there is provided a process for the production of a trichloroalkane derivative comprising reacting an alkene derivative with chloroform, characterised in that the process is initiated by photochemical cleavage of an initiator of formula (I):
Figure imgf000003_0001
wherein Z is chloro or fluoro; X is hydrogen, C,^ alkyl, C,_6 haloalkyl, -O-O-C(O)-Y or -O-O-Y; and Y is hydrogen, Cw alkyl or C^ haloalkyl.
Alkyl is straight or branched chain and is, for example, methyl, ethyl, w-propyl, w-butyl, H-pentyl, w-hexyl, .sO-propyl, /7-butyl, sec-butyl, wo-butyl, tert-butyl or «eø-pentyl. Haloalkyl groups are alkyl groups which are optionally substituted with one or more of the same or different halogen atoms. Halogen is fluorine, chlorine, bromine or iodine.
The photochemical cleavage of the initiator of formula (I), which is the result of absorption of an appropriate photon, results in the direct or indirect formation of the radical Z3C».
The process of the invention may provide higher yields of the trichloroalkane derivative and fewer by-products than corresponding processes, for example, those using thermal initiation, or photochemical processes performed in the absence of an initiator or with an initiator not having a trihalocarbonyl group. The three Z groups in the initiator of formula (I) may be the same or different. CZ3 may be, for example, CF2C1, however CZ3 is preferably CC13.
X is preferably Cw haloalkyl or -O-O-Y, wherein Y is Cw haloalkyl.
C,.6 Haloalkyl is preferably CF2C1, more preferably CC13. Preferred examples of initiators of formula (I) include 1,3-dichloro-l, 1,3,3- tetrafluoroacetone, chloral and, especially, hexachloroacetone.
The alkene derivative used in the process of the invention preferably has a terminal double bond.
The process of the invention is of particular use for the production of 4,4,4-trichlorobutane derivatives, as illustrated in Scheme I below, wherein Z and X are as described above for formula (I); W is C,^ alkyl, Cw alkenyl, OR1 or NR2R3; R1 is hydrogen, C,^ alkyl, C2.6 alkenyl, C6.l0 aryl or R4C(O); R2 and R3 are, independently, hydrogen, C,.6 alkyl, C^ alkenyl or C6.10 aryl; and R4 is C,.6 alkyl, C2.6 alkenyl, C6.I0 aryl, C,^ alkyloxy, C2.6 alkenyloxy or C6.I0 aryloxy.
Figure imgf000004_0001
(I)
CHC13 z3c-
(II)
Scheme I Alkenyl moieties may be in the form of straight or branched chains and, where appropriate, may be of either (E)- or (Z)-confιguration. Examples include vinyl and allyl. Aryl is phenyl or naphthyl. Therefore, in a preferred aspect of the invention the alkene derivative is a compound of formula (II):
,W
(II)
wherein W is C^ alkyl, C2.6 alkenyl, OR1 or NR2R3; R1 is hydrogen, C,.6 alkyl, C2.6 alkenyl, C6.,0 aryl or R C(O); R2 and R3 are, independently, hydrogen, C,.6 alkyl, C2^ alkenyl or C6.|0 aryl; and R4 is C,.6 alkyl, C2.6 alkenyl, C6.10 aryl, C,^ alkyloxy, C2.6 alkenyloxy or C6.,0 aryloxy.
Initiation of the process of the invention is preferably achieved by irradiating the reaction mixture with light of a wavelength of from about 200 to about 600nm, more preferably 200 to 350nm, for example a wavelength of 254nm. The light may be supplied by a low, medium or high pressure mercury lamp.
The reaction is preferably conducted at a temperature of about 0 to about 150°C and a temperature of from 25 to 150°C (such as 25 to 70°C) is particularly preferred.
The period of the reaction may be from about 30minutes to about 24hours, depending upon the volume of reactants and the temperature used. Generally a period of from about lhour to 12hours is sufficient.
Various further preferred features and embodiments of the present invention will now be described with reference to the following non-limiting example:
EXAMPLE 1 This Example illustrates various preparations of 4,4,4-trichlorobutanol and the tabulated results show the increased 'yield on conversion' obtained when using the process of the invention compared to the corresponding process in the absence of an initiator. The general procedure used in each case was the same: Chloroform was degassed for lhour with nitrogen immediately prior to use. A photochemical cell fitted with a condenser was charged with chloroform, allyl alcohol and (where appropriate) an initiator. The reaction mass was then degassed with nitrogen for a further 15minutes. The vessel was covered in aluminium foil and a uv screen was fitted. The reaction mixture was heated to the stated temperature using an oil bath, whereupon irradiation was carried out for the stated period of time, using light of the stated wavelength. Analysis of the reaction mixture was carried out by GC analysis.
The tables show the 'yield' of 4,4,4-trichlorobutanol (based upon the amount of allyl alcohol which was present as starting material); the 'conversion' of allyl alcohol (that is the percentage of allyl alcohol which was used up during the reaction); and the 'yield on conversion' (that is the yield of 4,4,4-trichlorobutanol when based upon the amount of allyl alcohol which was used up during the reaction): (% Yield on conversion) = (% yield of 4,4,4-trichlorobutanol) ÷ [(% conversion of allyl alcohol) ÷ 100]
Yield on conversion' is an important parameter since the larger its value, the smaller is the amount of unwanted by-products obtained from the reaction.
Results a) Reaction of chloroform with allyl alcohol (in the absence of an initiator).
Figure imgf000006_0001
b) Reaction of chloroform with allyl alcohol (using hexachloroacetone as initiator').
Figure imgf000006_0002
c) Reaction of chloroform with allyl alcohol (using 1, 3-dichloro-h 1,3.3- tetrafluoroacetone as initiator^
Figure imgf000007_0001

Claims

1. A process for the production of a trichloroalkane derivative comprising reacting an alkene derivative with chloroform, characterised in that the process is initiated by photochemical cleavage of an initiator of formula (I):
z3c X X 0) wherein Z is chloro or fluoro; X is hydrogen, C,^ alkyl, C,.6 haloalkyl, -O-O-C(O)-Y or -O-O-Y; and Y is hydrogen, C alkyl or C,^ haloalkyl.
2. A process according to claim 1, wherein CZ3 is CC13.
3. A process according to claim 1 or claim 2, wherein X is CC13.
4. A process according to any one of claims 1 to 3, wherein the alkene derivative has a terminal double bond.
5. A process according to claim 4, wherein the alkene derivative is a compound of formula (II):
,W
(ID
wherein W is Cw alkyl, CM alkenyl, OR1 or NR2R3; R' is hydrogen, Cw alkyl, C2.6 alkenyl, C6.10 aryl or R4C(O); R2 and R3 are, independently, hydrogen, Cw alkyl, C2.6 alkenyl or C6.10 aryl; and R4 is C,.6 alkyl, C2.6 alkenyl, C6.10 aryl, C,.6 alkyloxy, C2.6 alkenyloxy or C6.10 aryloxy.
6. A process according to any one of the preceding claims which is initiated by irradiating the reaction mixture with light of a wavelength of from about 200 to about 600nm.
7. A process according to claim 6, where the light is of a wavelength of from 200 to 350nm.
8. A process according to any one of the preceding claims, which is conducted at a temperature of about 0 to about 150°C.
9. A process according to claim 8, which is conducted at a temperature of from 25 to 150°C.
PCT/GB1999/003942 1998-12-09 1999-11-25 Process for preparing trichloroalkane derivatives WO2000034216A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP99956225A EP1137618A1 (en) 1998-12-09 1999-11-25 Process for preparing trichloroalkane derivatives
AU12868/00A AU1286800A (en) 1998-12-09 1999-11-25 Process for preparing trichloroalkane derivatives
JP2000586666A JP2002531537A (en) 1998-12-09 1999-11-25 Process for producing trichloroalkane derivatives
KR1020017007013A KR20010101129A (en) 1998-12-09 1999-11-25 Process for preparing trichloroalkane derivatives
IL14330699A IL143306A0 (en) 1998-12-09 1999-11-25 Process for preparing trichloroalkane derivatives

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9827133.1A GB9827133D0 (en) 1998-12-09 1998-12-09 Chemical process
GB9827133.1 1998-12-09

Publications (1)

Publication Number Publication Date
WO2000034216A1 true WO2000034216A1 (en) 2000-06-15

Family

ID=10843943

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1999/003942 WO2000034216A1 (en) 1998-12-09 1999-11-25 Process for preparing trichloroalkane derivatives

Country Status (8)

Country Link
EP (1) EP1137618A1 (en)
JP (1) JP2002531537A (en)
KR (1) KR20010101129A (en)
AU (1) AU1286800A (en)
GB (1) GB9827133D0 (en)
IL (1) IL143306A0 (en)
WO (1) WO2000034216A1 (en)
ZA (1) ZA200104182B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH271369A (en) * 1945-12-15 1950-10-31 Us Rubber Co A process for preparing a halogenated olefinic compound.
US4475003A (en) * 1982-09-13 1984-10-02 Basf Aktiengesellschaft Preparation of 1,1,1-trichloromethyl compounds
GB2303368A (en) * 1995-07-17 1997-02-19 Zeneca Ltd Trichlorobutyl acetate production
GB2315068A (en) * 1996-07-08 1998-01-21 Zeneca Ltd Preparation of 4,4,4-trichlorobutan-1-ol

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH271369A (en) * 1945-12-15 1950-10-31 Us Rubber Co A process for preparing a halogenated olefinic compound.
US4475003A (en) * 1982-09-13 1984-10-02 Basf Aktiengesellschaft Preparation of 1,1,1-trichloromethyl compounds
GB2303368A (en) * 1995-07-17 1997-02-19 Zeneca Ltd Trichlorobutyl acetate production
GB2315068A (en) * 1996-07-08 1998-01-21 Zeneca Ltd Preparation of 4,4,4-trichlorobutan-1-ol

Also Published As

Publication number Publication date
EP1137618A1 (en) 2001-10-04
AU1286800A (en) 2000-06-26
KR20010101129A (en) 2001-11-14
JP2002531537A (en) 2002-09-24
ZA200104182B (en) 2002-08-22
GB9827133D0 (en) 1999-02-03
IL143306A0 (en) 2002-04-21

Similar Documents

Publication Publication Date Title
Murray et al. Photosensitized oxidation of dialkyl disulfides
Node et al. Hard acid and soft nucleophile systems. 5. Ring-opening reaction of lactones to. omega.-alkylthio-or. omega.-arylthio carboxylic acids with aluminum halide and thiol
US4650913A (en) Sulfinate-initiated addition of perfluorinated iodides to olefins
WO2000034216A1 (en) Process for preparing trichloroalkane derivatives
US4093667A (en) Preparation of 4-n-hexylresorcinol
US5872290A (en) Preparation of acid chlorides
US3281440A (en) Fluorinated vitamin a compounds
CN1286247A (en) Process for preparing prolycopene and its intermediate
US2968673A (en) Chlorotolyl esters
EP0547092B1 (en) Process for preparing 2-methyl-3,5-dialkylpyridines by dealkylation with sulfur
US4670607A (en) Method for producing 2-(substituted aryl) propionaldehyde
US4306102A (en) P-Tert.butylbenzotribromide and p-tert.butylbenzoyl bromide and process for their manufacture
GB2125396A (en) Process for the manufacture of p-t-butyl-benzyl chloride
EP1013651B1 (en) O-(perfluoroalkyl)dibenzofuranium salt derivatives, intermediates for the preparation of the same, process for the preparation of the intermediates, perfluoroalkylating agents, and process for perfluoroalkylation
US3509210A (en) Preparation of dichloroacetyl chloride
US5091068A (en) Preparation of 3-trichloromethyl-pyridine
US3000930A (en) alpha-chlorotolyl benzoates
US4475997A (en) Process for preparing trichloroacrolein
CA1155455A (en) Intermediates in the preparation of cyclopropanecarboxylate esters and process for their manufacture
EP0019804A1 (en) Bromination of side chain of m-phenoxytoluene
US4754035A (en) Preparation of 2-alkylsulphonylalkylenepyrimidines
Yamato et al. Direct introduction of bromine onto the bridged methylene of 5, 13-di-tert-butyl-8, 16-dimethyl [2.2] metacyclophane
JPS5942339A (en) 2-aroyl-3-aryl-norbornadiene or -quadricyclane
JPH05132446A (en) Preparation of beta-halogeno-tert-alkylcarboxy- lic acid chlorides
HUT54336A (en) Process for producing 2-fluoro-1-olefins

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2000 12868

Country of ref document: AU

Kind code of ref document: A

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1999956225

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 143306

Country of ref document: IL

Ref document number: 200104182

Country of ref document: ZA

WWE Wipo information: entry into national phase

Ref document number: 1020017007013

Country of ref document: KR

ENP Entry into the national phase

Ref document number: 2000 586666

Country of ref document: JP

Kind code of ref document: A

WWP Wipo information: published in national office

Ref document number: 1999956225

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWE Wipo information: entry into national phase

Ref document number: 09857410

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 1020017007013

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 1999956225

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1020017007013

Country of ref document: KR