JPS62207233A - Production of 1-substituted 2-chloro-3,3,3-trifluoropropene - Google Patents

Abstract

PURPOSE:To efficiency obtain the titled compound useful as an insecticide or intermediate therefor, by reacting a 1-chloro-1,1-dihalotrifluoroethane with an aldehyde corresponding to the aimed compound in the presence of an electrophilic agent and zinc dust. CONSTITUTION:(a) A compound expressed by formula I (X<1> and X<2> are Cl, Br or I) is reacted with (b) a compound expressed by the formula RCHO (R is alkyl, aryl, alkenyl or H) in the presence of (c) an electrophilic agent and (d) preferably zinc dust activated with hydrochloric acid at -20-+100 deg.C, preferably 0-60 deg.C temperature to efficiently afford the aimed compound, expressed by formula II and useful as a fluorine-containing pyrethroid based insecticide or intermediate therefor from readily available raw materials. The amounts of the materials (a)-(d) are suitably as follows; 1.5-10, preferably 2-3 equivalents material (a) based on the material (c) based on the material (b) and 1.5-10 equivalents, preferably 2-3 equivalents material (d) based on the material (a).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a compound represented by the general formula % (1) (wherein R is an allekyl group, an aryl group, an alkenyl group, or a hydrogen atom). The present invention relates to a method for producing 1-substituted 2-chloro-3,3,3-1-lifluoropropene.

According to the method of the present invention, 3-(, (2-chloro-3,3,3-F-lifluoro-1-propenyl)-2, which has a wide range of uses as a fluorinated pyrethroid insecticide, for example,
2-dimethylcyclopropanecarboxylic acid ester (JP-A-53-95945.54-112820.54-13
0537.55-59141.55-89248.55
-111488), and its synthetic intermediate 2-
Chloro-1,1,1-)lifluoro-5-methyl-2,
4-Hexadiene can be produced.

[Conventional technology]

Conventionally,! -Substituted 2-chloro a-3,3,3-trifluoropropene is synthesized by (i)
．． 1.1-) Method of adding dihalotrifluoroethane and then dehydrohalogenation (4!F 1989-959)
45.54-112820.55-89248゜56-
However, in this method, the synthesis of starting materials is often complicated, and the addition yield is often low.

On the other hand, 2,2-dimethyl-3-(2-chloro-3,3,
The method for synthesizing 3-trifluoro-1-propenyl) cyclopropanecarboxylic acid ester is as follows: (i) After adding 3,3-dimethyl-4-pentenoic acid dyad 1,1,1-trichlorotrifluoroethane, cyclization,
Method of dehydrohalogenation (JP-A-53-95945.
54-112820゜55-89248 ), (isu1
．． 1.1-4lifluoro-2-chloro-5-methyl-2
, 4-hexadiene or 1.1.1-trifluoro-
Synthesis method from 2,2-dichloro-5-methyl-4-hexene and diazoacetic acid ester (JP-A-53-9594)
5゜54-112820, J, Mol, σ16.
119 (1981)), the ring reduction reaction of (, (・5tt)z-chloro-2-(2,2-dichloro-3゜3.3-trifluoropropyl)-3,3-dimethylcyclobutanone. How to use (Japanese Patent Application Laid-Open No. 56-92830)
, Gtv) 6-(1-1-dihalotrifluoroethyl)-4,4-)lf-ru-l-oxabicyclo(3,
1,0) Method for reducing hexen-2-one with zinc (US
Pat, 4,235,780) is known.

However, both methods require a large number of steps, and (ii
Methods () and (iv) have the disadvantage that they are difficult to implement industrially because the synthesis of raw materials is complicated.

[Problem that the invention seeks to solve]

The present invention overcomes the problems of the prior art and the general formula (I
) was developed in order to provide a method for producing the compound represented by formula (2) more efficiently.

[Means for solving problems]

The present invention relates to l-chloro-1,1- represented by the general formula ÷ C1-C-CF;
Dihalotrifluoroethane and general formula mK (a)
□[1] (In the formula, 0 is an alkyl, aryl, alkenyl group, or a hydrogen atom) with an aldehyde represented by the above general formula CD, characterized in that it is reacted in the presence of an electrophile and zinc dust. This is a method for producing a compound represented by

1 represented by the above general formula (II) which is a raw material of the present invention
, 1.1-) Dihalotrifluoroethane is an industrially easily available compound, such as 1,1゜1-trichlorotrifluoroethane, t-bromo-1,1-dichlorotrifluoroethane, l, 1-dibromo-1-dichlorotrifluoroethane% 1Il-dichlorotetrafluoroethane, 1-bromo-1-chlorotetrafluoroethane,
l-Iodozu-1, 1-'-'ir-trifluoro-ethane, etc. can be used. The other raw material, the aldehyde represented by the general formula (1), is often industrially easily available (Chem, Ind., (London) 199 (19
84)) 0 For example, it can be produced in high yield by ozonolysis and reduction of chrysanthemum acid ester (Japanese Patent Application No. 1983-
214783). Examples of these aldehydes include methyl 2.2-dimethyl-3-formylcyclopropanecarboxylate, ethyl 2.2-dimethyl-3-formylcyclopropanecarboxylate, and 2.2-dimethyl-3-formylcyclopropanecarboxylate. -butyl, phenyl 2,2-dimethyl-3-formylcyclopropanecarboxylate, benzyl 2,2-dimethyl-3-formylcyclopropanecarboxylate, 2,2-dimethyl-3-formylcyclopropanecarboxylate (2-methyl -3-phenylphenyl)methyl, 2,2-dimethyl-3-formylcyclopropanecarboxylic acid 3-pheno-LL/xif I-←4methyl, 2,2-dimethyl-3-formylcyclopropanecarboxylic acid cyano(3 -phenoxyphenyl)methyl, 2,2-dimethyl-3-formylcyclopropanecarboxylic acid pentafluorophenylmethyl,
hexanal, cyclohexanecarboxaldehyde,
2-phenylpropanal, isobutyraldehyde, cinnamaldehyde, crotonaldehyde, 3-methyl-
2-butinal, benzaldehyde, viropenal, p
-40 lobenzaldehyde, furfural, etc. can be used.

The molar ratio of the compound used []] and (1) is CI / (
1)=0.5-10, preferably 1-3, the reaction can be carried out efficiently. Although commercially available zinc powder may be used directly, it is preferable to use one activated with hydrochloric acid. The appropriate amount to use is 1.5 to 10 equivalents, preferably 2 to 3 equivalents, based on (1).

In the present invention, the reaction is carried out in the presence of an electrophilic agent. Examples of electrophilic agents include acid anhydrides such as acetic anhydride, benzoic anhydride, trifluoroacetic anhydride, methanesulfonic anhydride, and acid halogens such as acetyl chloride, acetyl bromide, benzoyl chloride, methanesulfonyl chloride, and p-toluenesulfonyl chloride. carbonaceous esters such as diethyl carbonate, chloro9ic acid esters such as ethyl phosphate and benzyl chlorosate, metal chlorides such as silicon tetrachloride, titanium tetrachloride, aluminum chloride, tin tetrachloride, and chlorotrimethylsilane. etc. can be used. The appropriate amount to be used is 0.1 to a large excess, preferably 0.2 to 2 equivalents, relative to I].

The zinc dust and electrophile used in this reaction can be added to the reaction system from the beginning, but please note (1)
After reacting (1) and (1) with about 1 equivalent of zinc dust, the yield can be improved by adding the remaining zinc dust and electrophilic agent.

In the present invention, the reaction can be carried out efficiently by adding a transition metal compound. The transition gold) J compounds used include CuCl, CuI, CuCl2. CuBr
2°Cu(acac)2 (copper(1) acetylacetonate).

Copper or silver salts such as Ag0Ac, NiC1, N1Cl2
(PPh3)2°NiC12(C)1,0N)2. Ni
(PPh3)4. PdC12, Pd(OAc)2゜PdC1(PPh), Pd(PPh,)4 etc.
Group transition metal compounds can be used. A so-called catalytic amount is sufficient for the amount used. - In the present invention, the reaction can also be carried out efficiently by carrying out the reaction under ultrasonic irradiation.

An ultrasonic output of 400 W or less is sufficient.

The reaction is preferably carried out in an aprotic solvent, and for example, amides such as dimethylformamide and hexamethylphosphoric triamide, sulfoxides such as N,N-dimethylpropylene ureas, and dimethyl sulfoxide can be used. It may be used in combination with a common aprotic organic solvent.

The reaction proceeds at -20°C to 100°C, but preferably at 0°C to 60°C for efficient reaction.The present invention will be explained in more detail with reference to Examples below.Example 1 3-formyl-2, 2-dimethylcyclopropanecarboxylic acid (2-methyl-3-phenylphenyl)methyl 6
A solution of 444 (2,0 Ommol) in 2 ml of DMF was added with 0.36 WLt of trichlorotrifluoroethane (3,0 mmol).
Ommol), zinc powder 196my(3,00mmol)
) and stirred at 50°0 for 5 hours. Acetic anhydride 0.3
sl, 196 mp (3, ooq) of zinc powder was added, and the mixture was further stirred at 50"O for 12 hours. After adding water and a small amount of hydrochloric acid, ether extraction (5aj x 4) was performed. The extract was diluted with anhydrous magnesium sulfate. After drying, it was filtered and concentrated under reduced pressure.The obtained crude product was subjected to column chromatography (
Silica gel, dichloromethane-hexane 1;3-1;2
) to produce colorless oily 3-(2-chloro-
3,3,3-trifurol-1-propenyl)-z,
z-dimethyll dichlorofuropanecarvone fi (2-
MethyIre-3-phenyIlephenyl)methyl 419# was obtained. Yield 50es.

φ): @: 6: t.

'H-NMR (CDCI3): (for Zl-isomer ic, 7
:, JL, 23 (8° 3H), t, 35 (s, 3H),
1.82 (d, tH).

2.22 (S, 3H), 2.42 (dd, IH), 5.
20(5,2H), 6.1O(d(1,LH), 7.1
5-7.5 (m, 5fl).

(E) For unity, Jl, 23(s, 3) 1).

1.29 (S, 3H), 5.85 (d, exit)
Other signals cannot be distinguished from (Z) bodies.

"F-NMR ((??DCI-CFCI5): (Z) Heck, J 68-7 (sl.

(G) Integrity, a 62.5 (8).

IR, (neat):1732.12B4.122B,
1187°1144.1116.765,707crI
L.

Example 2 3-methyl-2-butynal 84q (1,ommot
) in the DMFld solution of 1.1. L-1 Licrotrifluoroethane 0.142d (1.20mmol), zinc dust 72g (1.1Ommol), dichlorobis(triphenylphosphine) palladium l 3"l (0.02
mmo 1 ) was added thereto, and the mixture was stirred at room temperature for 1 hour and at 50° C. for 24 hours. Zinc powder 131tayC2, Ommol)
, 0.15% of acetic anhydride was added, 1 m of water was stirred for further 4 hours at 50°C, and a small amount of hydrochloric acid was added, followed by ether extraction. 19Bv-scale quantitative determination (Bi part 1 standard: 1, 3, 5- IJ Krollo 2.4.6-
The yield of 2-chloro-1-trifluoro-5-methyl-2°4-hexadiene was determined using 1-lifluorobenzene). Yield: 53 cm.

z): However) = 88:12゜') l-NMR (CDC13): (For Z1 body,
r, itl, 87 (8°3H), 1.96 (s, 3H)
, 8.13 (d, J=11.1Hz, 1)i) ,
7.01 (d, J=l 1.1Hz.

xH).

For one body, a 6.83 (d , J=l 1.I
Hz, IH).

19F-NMR (CDCI-CFCl2): (J69.0 for Zl form (51° for integral, sz, x(s).

Example 3 D of 3-methyl-2-butynal 84 Akebono (1 mmol)
Add 0.142 m (1.2 mmol) of 1.1.1-trichlorotrifluoroethane and 72 μm (1.1 mmol) of zinc powder to the MF lat solution, and heat at 50°.
Ultrasonic waves were irradiated at C-60°C for 4 hours. Acetic anhydride 0.1
5 m/2, and 130 q (2.0 mmol) of zinc powder were added thereto, and ultrasonic waves were further irradiated at 50° C. for 2 hours. below,
The yield of 2-chloro-1,1,1-1-refluoro-5-methyl-2,4-hexadiene was determined in the same manner as in Example 2.

Yield 41%. (A): (Uniform = 7:3° Example 4 Benzaldehyde 106% (1,00mmo 1 ) c
r) DMFo, 5ml1fn liquid with zinc powder 1951! II
c 3.00 mmol turbid, trichlorotrifluoroethane 0.236 ml (2.0 mmol)
Acetic anhydride 0.142M (1.5 mmol) Processing 0
The mixture was stirred for 1.5 hours at room temperature for 5 hours. Zinc dust 20n
oL rny (o, a t→-1 was added and stirred at 50°C for 2 hours. 2Mt of saturated ammonium chloride aqueous solution was added,
Extracted with hexane (3x3d). The yield of l-phenyl-2-chloro-3,3,3-1-refluoro-1-propene was determined by GLC analysis.

Yield: 53 pieces. (a):ni)=8:l.

'H-NMR (cDc15): J 7.2-7.
5 (m, 4H), 7.5-7.8 (m, zH).

13T! - J69.3 (d, J = 0.8Hz
, 3F).

For the reviewer, J62. l(s, 3F).

IR(neat): 1307, 1216, 1176
, 1140.

962.692cIrt.

Mass (rr% Zheng)): 208 (M +2, 34
), 207 (M+++ 1.10), 206 (M+, 1OO), 171 (39)
, 151(59), 102(16), 75(ll), 5
1 (15), 50 (10) - Elemental analysis value: C, H6C
Calculated value for lF3: C, 52,32; H, 2,93
blood.

Actual measurement t: 0.52-05. H, 2,89%.

Example 1 Example 5 Hensfur f'hi)' 1064 (1,00 mmol
>17) Add 1.1. to DMF11 solution. l-) Lichlorotrifluoroethane 0.24s+j (2.0mmol),
Zinc dust 320m9 (4,90mnol acetic anhydride 0.1
4 m (1.5 mmol) was processed and stirred at 50°C for 7 hours. After adding 1 mg of water and a small amount of hydrochloric acid, the yield of 2-chloro-313,3-) refluorol-1-phenylpropane was determined by 019F-NMR quantification after ether extraction.The yield was 75qI! I, ■): Invasion) = 8
6:14゜Example 6 Benzaldehyde 105f105ffII (0-99)
1.1 in DMF 1-solution. Add 0.142 m (1.2 mmol) of l-trichlorotrifluoroethane and 72 W (1.1 mmol) of zinc powder, and stir at room temperature for 1 hour.
Stirred at 0"O for 24 hours. Zinc dust 131Wjg (2,
0 mmol), add 0.15- acetic anhydride, and heat at 50°C.
The mixture was further stirred for 4 hours.

After adding 1-1 portions of hydrochloric acid to water, ether extraction was performed. “2-chloro-3, by F-N?vlR quantification,
The yield of 3,3-trifluoro-1-7enylpropene was determined. Yield: 78 cm.

(4):ni)=87:i3゜Example 7 Benzaldehyde 106f! 19 (1,00 mmol
) in 1 m of DMF 1.1. l-) Lichlorotrifluoroethane 0.2411/(z, ommol)%
Add zinc powder 3254 (5.0 mmol) and stir at room temperature for 10
After stirring for a minute, titanium tetrachloride 0.12 m (1.6 mmol
) and add a small amount of it. 0.5 hours at room temperature, 2 hours at 50℃
After stirring for an hour, water 2-1 and a small amount of hydrochloric acid were added. After ether extraction, 2-chloro-3,3,3-
The yield of trifluoro-1-phenylpropene was determined.

Yield 67%. (Z):@=9:l.

Example 8 DMF ld bath solution of benzaldehyde 106”? (1,00 mmol), silicon tetrachloride* 0.034 sl (
0.3 mmol) was added thereto, and the mixture was stirred for a while at room temperature.

1,1,1-trichlorotrifluoroethane 0.18m
(1.5 mmol), zinc dust 196sF (3.0 mm
After stirring at 0°C for 1 hour and at 50°C for 2 hours, 2su of water and a small amount of hydrochloric acid were added to stop the reaction. After ether extraction, 2-chloro-3
, 3,3-trifluoro-1-phenylpropene was determined.

Yield 67%. (Z) Two reviews = 8: 10 Example 9 p-chlorobenzaldehyde 139 hits (0,99 m-m
ol) in DMF, -Solution number: acetic anhydride 0.14a/(
1,5""'), l*l*l-to'J black o) IJ7/L/Oaztan0.24m
(2-Ommo 1 ), zinc powder 328yv (5,0
mmol) and stirred at 0°C for 10 minutes and at 50°C for 4 hours. Add 10s of water + 7 and extract with ether (10dX
3) was carried out. The extract was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. A thin layer of the obtained crude product a
Purification by mudgraphy (silica gel, dichloromethane-hexane 1:2) gave 175 ml of colorless oily 2-chloro-3,3,3-)7I rheol-r-(4-chlorophene I)flopen. Yield: 73 cm.

12(t)=88:12°bp: 75°C/1 mm') l-NMR (CDCI, ): (JT, 25(s, LH) for Z1 body.

7.40 (d, J=r OHz, zH), 7
．． 67 (d, J=10Hz, 2H), 7.67 (d
, J=10Hz, 2H).

19F-CFC1 (CDCI-CFCl, ): (A) For body, J6.9.1° For plow body, a61. 'l.

IR (neat): 1495, l 307, 12
88, 1 k73.

1140.1106,962c*.

Example 10 Biperonal 51 #ll (1,01 mmol)
t, t, t-trichlorotrifluoroethane (0.142 ml C1.2 mmol) in 1 ml DMF solution of
72q (x, tmmot) of zinc powder was added, and the mixture was stirred at room temperature for 1 hour and at 50°C for 24 hours.

Zinc dust 13 xq (z, Ommo f )% acetic anhydride 0
．． 15 ml was added thereto, and the mixture was further stirred at 50°C for 4 hours. Hereinafter, in the same manner as in Example 9, colorless oily 2-chloro-3,
3.3-Trifluoro-1-(2,3-methylenedioxyphenyl)propene 2034 was prepared. Yield: 81.

φ)=に)=85:15゜bp:roυ(bath t
em9)/Q, 1mm'HJJMR (CDCI,
) : For (Z) body, J6.03(s.

2) 1), 6.7-7.4 (m, 4H).

(g) 6.00 (S, 狽) for the body.

IIL (neat): 1507, 1496, 1450
,1291,! 1262.1251,1174,11
33°1040cWL.

Mass(rrVz(%)) zsz(M++z,
34), 25t (M++1,39), 250
(M+, 100), 249 (87), 157 (26),
137(16).

107(12), 87(12), 63(11).

62(13).

Elemental analysis value: c1oH6clF30□2 vs. city calculation value:
C, 47,93; H, 2,41ch.

Actual value: C, 47,81;) 1,2.47%.

Example 11 D of biveronal l 5ony (1,00 mmol)
MF 1m solution 1.1.1-)licro-O trifluoroethane 0.14m (1,2mm0I), zinc powder 72Q
(1.1 mmol) was added and stirred at 50°C for 12 hours. 131η (2,0 mmol) of zinc dust and acetyl chloride Q, 1- were added, and the mixture was further stirred at 50°C for 12 hours.

After adding 2 ml of water and extracting with ether, 2-chloro-3,3,3-)refluoro-1-(2
, 3-methylenedioxyphenyl)propene was determined. Yield 63%. (A):@=86:14゜Example 1
2 Cinnamic aldehyde 1321Fv (1,00mm0 l
) in DMF t-solution with 1.1.1-trichlorotrifluoroethane 0. Zinc powder 130119 (2, Ommol) was added with Zinc powder 72'FC1, 1 mmol) and stirred at 50°C for 21 hours.
, 0.15% of acetic anhydride was added, and the mixture was further stirred at 50°C for 4 hours. After adding zd% of water and a small amount of hydrochloric acid, ether extraction was performed. Thereafter, in the same manner as in Example 9, 4-chloro-5,5°5-trifluoro-1-phenyl-1,3-pentadiene 167 cape was obtained as a colorless oil. Yield: 72 cm.

(A): (E): 89: 1 t.

bp: 60-70℃ (bath temp) 10.1m
m.

"H-NI114R(CI)01s)a 6-6-
7.2 (m-2kl), 7-2-7.6 (m.

6H).

” 'F-Nlla (CDCI3): J 6 g, 5(s) for the (Z) body.

(6) 761.8 (S) for the body.

IR (neat): 1634.1311, 1292,
1240°1188.1136,970.945,74
9゜690CIE.

Mass (+11/zi%): 234 (M +2.1
7), 232 (M+.

+50), 197(31), 178(14), 177(1
00), 146(10), 129(14).

128(61), 127(16), 77(10).

63(11), 51(15).

Elemental analysis value: 3.49 for C1, H8CIF, calculated value: C, 56,79:H, Toko←4゜Actual value: C,
56,74;)i, 3.25chi.

Example 13 Cyclohexanecarboxaldehyde 112rnp(1
,00 mmol) in a DMFtM solution of 1.1.1-1-
Lichlorotrifluoroethane 0.142m (1,2mm
ol), Zinc powder 72QC1, 1 mmol), Zinc o
a bis (triff.

Nylphosphine) Nickel 13 (0.02 mmol
) and stirred at room temperature for 1 hour and at 50°C for 24 hours.

Zinc dust 1314 (2,0 mmo 1), acetic anhydride 0
．． 15 m of the mixture was added, and the mixture was further stirred at 50°C for 4 hours. Hereinafter, in the same manner as in Example 2, 2-chloro-3,3,3-1
The yield of -refluoro-1-cyclohexylpropene was determined. Yield 50%. (Z):(T):85:15゜'
f(-NMR(CDCl2)IZ)integratedGCCDC,J
l, O-2,3 (m, l0H), 2.3-2.8 (m,
LH), 6.30 (d, J = 9Hz, LH)
.

(b) For one body, 6.05 (d, J=9)1
z.

lH).

"F-NMFL (CDCl 3-CFC13):
For one piece, δ69.2(S).

■62.2 (S) for one unit.

IR(neat):2945,2870,1293,1
184°1140CI! L.

Elemental analysis value: Calculated value for C2H1□CUF:
C, 50, 84; H, 5-69ch.

Actual measurements: C, 50,82; H, 5,64.

Claims (1)

[Claims] (1) 1-chloro-1,1-dihalotrifluoroethane represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and an aldehyde represented by the general formula RCHO in the presence of an electrophile and zinc dust. The general formula RCH=C(Cl
)CF_3 (wherein R is an alkyl group, aryl group, alkenyl group or hydrogen atom, and X^1
and X^2 is a chlorine atom, a bromine atom or an iodine atom. ).