JP2002531537A - Process for producing trichloroalkane derivatives - Google Patents

Abstract

(57) Summary According to the present invention, the method comprises reacting an alkene derivative with chloroform, wherein Z is chloro or fluoro; X is hydrogen, C _1-6 alkyl , C _1-6 haloalkyl, —O—O—C (O) —Y, or —O—O—Y; and Y is hydrogen, C _1-6 alkyl, or C _1-6 haloalkyl. Provided by a photochemical cleavage of an initiator represented by the formula: The production method of the present invention is particularly useful for producing 4,4,4-trichlorobutane derivatives.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a photochemically initiated addition of chloroform to an alkene derivative (p
The present invention relates to a method for producing a trichloroalkane derivative by photochemically initiated addition. The process of the present invention is particularly useful for producing 4,4,4-trichlorobutane derivatives, which are important intermediates and products in the chemical industry. The 4,4,4-trichlorobutane derivatives are useful as intermediates in the production of pesticidal compounds of the type described, for example, in WO 95/24403. 4,4,4-Trichlorobutane derivatives can also be used as intermediates in the preparation of compounds having useful solvent properties.

According to the present invention, the method comprises reacting an alkene derivative with chloroform, wherein the compound of formula (I)

[0003]

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Wherein Z is chloro or fluoro; X is hydrogen, C _1-6 alkyl, C _1-6 haloalkyl, —O—O—C (O) —Y, or —O—O— Y; and Y
Is a hydrogen, C _1-6 alkyl, or C _1-6 haloalkyl), which is initiated by photochemical cleavage of an initiator represented by the formula:

[0005] Alkyl is straight or branched and includes, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert- Butyl or neopentyl.

[0006] Haloalkyl is an alkyl group optionally substituted with one or more identical or different halogen atoms. Halogen is fluorine, chlorine, bromine, or iodine.

[0007] As a result of the photochemical cleavage of the initiator of formula (I) (caused by the absorption of a suitable photon), the radical Z ₃ C. is formed directly or indirectly. The manufacturing method of the present invention is based on a corresponding process (e.g., thermal initiation).
The yield of the trichloroalkane derivative is higher and the by-products (by-produ) are higher than in the case of the process using an initiator or a photochemical process performed in the absence of an initiator or with an initiator having no trihalocarbonyl group.
It can be said that the generation of cts) is small.

The three Z groups in the initiator of formula (I) may be the same or different.
CZ ₃ may be, for example, CF ₂ Cl, but is preferably CCl ₃ . X is preferably C _1-6 haloalkyl or —O—O—Y, wherein Y is C _1-6 haloalkyl.

C_1-6Haloalkyl is preferably CF_TwoCl, more preferably CCl _Three It is. Preferred examples of the initiator of the formula (I) include 1,3-dichloro-1,1,3,3-
There are tetrafluoroacetone, chloral, and especially hexachloroacetone
.

The alkene derivative used in the production method of the present invention has a terminal double bond (ter
It is preferable to have a minor double bond. The production method of the present invention comprises 4,4,4-trichloro
Particularly useful for the production of butane derivatives. In Scheme I, Z and X are
W is as described above for formula (I);_1-6Alkyl, C_2-6Alkenyl
, OR¹Or NR^TwoR^ThreeAnd R¹Is hydrogen, C_1-6Alkyl, C_2-6Alkenyl
, C_6-10Aryl or R^FourC (O); R^TwoAnd R^ThreeAre independent of water
Elementary, C_1-6Alkyl, C_2-6Alkenyl, or C_6-10Aryl; and R ^Four Is C_1-6Alkyl, C_2-6Alkenyl, C_6-10Aryl, C_1-6Alkyloxy
, C_2-6Alkenyloxy, or C_6-10Aryloxy.

[0011]

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The alkenyl moiety may be in either a straight or branched form and, where appropriate, in either the ( E )-or ( Z ) -configuration. Examples include vinyl and allyl.

Aryl is phenyl or naphthyl. Thus, in a preferred embodiment of the present invention, the alkene derivative is of the formula (II)

[0014]

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Wherein W is C _1-6 alkyl, C _2-6 alkenyl, OR ¹ or NR ² R ³ ;
R ¹ is hydrogen, C _1-6 alkyl, C _2-6 alkenyl, C _6-10 aryl, or R ⁴
R ² and R ³ are independently of each other hydrogen, C _1-6 alkyl, C _2-6 alkenyl, or C _6-10 aryl; and R ⁴ is C _1-6 Alkyl, C _2-6 alkenyl, C _6-10 aryl, C _1-6 alkyloxy, C _2-6 alkenyloxy, or C _6-10 aryloxy).

In order to start the production method of the present invention, light having a wavelength of about 200 nm to about 600 nm is preferably applied, more preferably, a wavelength of 200 nm to 350 nm (for example, 254 nm).
The reaction mixture is irradiated with light having a wavelength of The light can be supplied by low, medium or high pressure mercury lamps.

The reaction is preferably carried out at a temperature of from about 0 ° C. to about 150 ° C., particularly preferably at a temperature of 25 to 150 ° C. (eg 25 to 70 ° C.). Reaction times are from about 30 minutes to about 24 hours, depending on the amount of reactants and the temperature used. Generally, about 1 hour to about 12 hours is sufficient.

Hereinafter, still other preferred features and embodiments of the present invention will be described with reference to Examples, but the present invention is not limited by these Examples. Example 1 This example demonstrates various preparations of 4,4,4-trichlorobutanol.
The indicated results show that the use of the process according to the invention increases the "yield on conversion" compared to the corresponding method without initiator.

The general procedure used in each case was the same: Chloroform was degassed with nitrogen for 1 hour immediately before use. Chloroform was added to a photochemical cell equipped with a condenser.
Allyl alcohol and, where appropriate, initiator were charged. The reaction mass was degassed with nitrogen for another 15 minutes. The container was covered with aluminum foil and fitted with a UV screen. The reaction mixture was heated to the temperature using an oil bath and then irradiated using light of the wavelength over the time. Analysis of the reaction mixture was performed by GC analysis.

The table below shows the “yield” of 4,4,4-trichlorobutanol.
(Based on the amount of allyl alcohol present as starting material); "conversion" of allyl alcohol (ie, percent of allyl alcohol used in the reaction); and "conversion yield" (ie, , The yield of 4,4,4-trichlorobutanol based on the amount of allyl alcohol used in the reaction). (Conversion yield%) = (4,4,4-trichlorobutanol yield%) ノ ー ル [(Allyl alcohol conversion%) ÷ 100] The conversion yield is an important parameter. Because the larger the value,
This is because the amount of undesirable by-products obtained from the reaction is reduced. result

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), 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 (72 ) Inventor Jackson, David Anthony West Yorkshire, H.21 21 UK, Huddersfield, Leeds Road, Zeneca Huddersfield Works, Process Technology Department, P.O. Box A 38 F term (reference) 4H006 AA02 AC30 BA93 BA95 BC10 EA02

Claims (9)

[Claims] 1. A method comprising reacting an alkene derivative with chloroform, comprising reacting an alkene derivative of formula (I) Wherein Z is chloro or fluoro; X is hydrogen, C _1-6 alkyl, C _1-6
Y is haloalkyl, —O—O—C (O) —Y, or —O—O—Y;
Is hydrogen, C _1-6 alkyl or C _1-6 haloalkyl), which is initiated by photochemical cleavage of an initiator represented by the formula: 2. The method according to claim 1, wherein CZ ₃ is CCl ₃ . 3. The method according to claim 1, wherein X is CCl ₃ . 4. The alkene derivative has a terminal double bond.
The production method according to any one of claims 1 to 4. 5. The alkene derivative of the formula (II) Wherein W is C _1-6 alkyl, C _2-6 alkenyl, OR ¹ , or NR ² R ³ ; R ¹ is hydrogen, C _1-6 alkyl, C _2-6 alkenyl, C _{6 -10} aryl or R ⁴ C be a (O); R ² and R ³ is each independently of the other hydrogen, C _1-6 alkyl, C _2-6 alkenyl or C _6-10 aryl; and R ⁴ is C _1-6 alkyl, C _2-6 alkenyl, C _6-10 aryl, C _1-6 alkyloxy, C _2-6 alkenyloxy,
Or C _6-10 aryloxy). 6. The method according to claim 1, wherein the method is started by irradiating the reaction mixture with light having a wavelength of about 200 nm to about 600 nm. 7. The method according to claim 6, wherein the wavelength of the light is from 200 nm to 350 nm. 8. The method according to claim 1, which is carried out at a temperature of about 0 ° C. to about 150 ° C. 9. The method according to claim 8, which is performed at a temperature of 25 ° C. to 150 ° C.