JPS6124596A - Preparation of halogen-substituted ethylene derivative - Google Patents

Abstract

PURPOSE:To obtain the titled compound such as a trifluorovinyl-containing monomer for a fluorine-containing functional polymer, under mild condition, in high yield, by reacting a vinylsilane having a specific structural formula with an aldehyde in the presence of a fluorine-ion source. CONSTITUTION:The objective compound of formula II [e.g. (1-phenyl-2,3,3-trifluoro-2-propenyloxy)triethylsilane] can be prepared by reacting (A) a vinylsilane of formula I (R<1>-R<3> are halogen, H, alkyl, aryl, aralkyl, etc.; R<1> and R<3> may together form an aromatic ring; at least one of R<1>-R<3> is halogen; R<4>-R<6> are alkyl, aryl, etc.) with (B) an aldehyde of formula RCHO (R is H, alkyl, aryl, aralkyl, etc.) in the presence of (C) a fluorine ion source [e.g. tris (diethylamino) sulfonium difluorosilicate], preferably in a solvent, preferably at -20-50 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the general formula (wherein I(-i alkyl group, aryl group, aralkyl group, alkenyl group or water; +, atom, 1 is also 1.1
42, l73 is a halogen atom, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an acyloxy group, an alkoxy group, an amino group, a thio group, a noano group
In particular, it is an alkoxycarbonyl group, and together with the carbon bonded to R''1312, it can form an aromatic ring.

At least one of R1, R2, and R3 is a halogen atom. H, 4, H, S, and 1 mo are an alkyl group, an aryl group, an aralkyl group, or an alkenyl group. ) relates to a method for producing a halogen-substituted ethylene derivative.

According to the method of the present invention, a single fluorine-containing polymer having properties such as water and oil repellency, ion exchange properties, radiation sensitivity, cough substance permeability, piezoelectricity, etc.] can be synthesized in various ways.

As a method for synthesizing compounds with a trifluorovinyl group, trifluorovinyl riborum 4 is prepared from chlorotrifluoroethylene and bunallithium.
8. Search for aldehydes, keto/carbon dimides, etc.-J11
1 and anti-LL, a method is known [J.

srg, Uhem-, 28, 839 (1963); J.
Org.

;', I'etrabedron Left, +24
+5615 (1983)]. However, these methods require the preparation of trifluorovinyl lithium and the reaction with an electrophilic agent to be carried out at extremely low temperatures, resulting in drawbacks such as impossibility of practical production methods and i-L.

As a result of our efforts to overcome these conventional drawbacks, the present inventors have discovered a method for producing the halogen-substituted ethylene derivative represented by the general formula CI] under warm conditions and in good yield. The invention has been completed.

In the present invention, in the presence of a fluorine anion, the general formula (wherein R1, 1L2, R' (4 halogen atoms, hydrogen atoms, alkyl groups, aryl groups, aralkyl groups, alkenyl groups &, acyloxy groups, alkoxy group, amino group, thio group, /ano group or alkoxycarbonyl group, and LLl and R
3 together with the bonded carbon forms an aromatic ring. At least one of 1, R2, and 3 is a halogen atom.

R', R5 and R6 are an alkyl group, an aryl group, an aralkyl group or an alkenyl group. ), it becomes nylsilane with the general formula, ■i -C)(O-(nl) (wherein 几(1 is an alkyl group, aryl group, acyloxy, alkenyl group or hydrogen atom) and six The above general formula [
A halogen-substituted ethylene derivative represented by [I] is produced.

The vinylanlan represented by the general formula [11], which is the raw material of the present invention, can be obtained by a method (ArLgew) in which vinyl chloride and jinran are inversely compared in the presence of a palladium catalyst.
, Chem, Int, Ed-Engl, 17+
279 (H178)), (11) The corresponding ethylene derivative and hydrorane are reacted in the presence of a ruthenium catalyst.
'M, How to make G (people ngew, Chem, In
t, lad, gngl.

±Island 928 (1980) #Sho) + (++i)
The method of reacting the corresponding vinyl chloride with chlorosilane and metal magnesium, (J, Urganomet,
Chem, +7L 377 (1974))
(iv) A method of reacting the corresponding vinyllithium with p-rosilane (J, Org.

Cherrb, 33+ 472 (1968);T
etrahedron Lel.

24, 5615 (1983); Japan Chemical Society of Japan 47th Spring Annual Meeting Presentation t↓ Collection, lG26 (1983) Tanitsu), for example, trimethylsilyltrifluoroethylene, triethylsilyltrichloroethylene, dimethylphenyldilyltrifluoroethylene, methylphenylsilyltrifluoroethylene, dimethylvinylsilyltrifluoroethylene, dimethylbenylsilyltrifluorooxfvn, 1-)') ethylsilyl-1,2-difluoroethylene, 1 -triethylsilyl-1,2-difluoro-1-hexene, 1-trimethylsilyl-1,2
-3-dimethyl-1-butene, 1-triethylsilyl-2-ethylthiodifluoroethylene,
2-triethylsilyl-1,2-difluoroacrylonitrile, 1-triethylsilyl-2-methoxyfluoroethylene, 1-triethylsilyl-1-chlorodifluoroethylene, 1-triethylsilyl-1-bromodifluoroethylene, triethylsilyltrichloroethylene, 1-triethylnoryl-2,2-difluoroethylene 2-) ethylunryl-3-fluoroacrylic methyl, β-triethylsilyl-α, β-difluorostyrene, 1-)! J Ethylsilyl-1,2-difluoropenta-1,3-diene, 1-triethylsilyl-1
, 2-7fluoro3-phenyl-1-propene, trimethylsilylpentafluorobenzene, dimethylphenylsilylpentafluorobenzene, 1-)rimenarunyl-2.3.5.6-tetrafluorobenzene, 1-trimethylsilyl-4-butyltetrafluoro benzene,
1-trimethylsilyl-4-methoxy7tetoxyfluorobenzene, 1-trimethylsilyl-4-dimethylaminetetrafluorobenzene, 1-trimethylsilyl-2,6
-difluorobenzene, 1-trimethylsilyl-2,4
,6-)lifluorobenzene, 1-trimethylsilyl-
3゜5-dichlorotrifluorobenzene, trimethylsilylpentachlorobenzene, trimethylsilylpentabromobenzene, 2-trimethylsilyl-1,3,4-)
Lifluoronaphthalene, 2-trimethylsilyltrifluorofuran, 2-trimethylsilyltrifluorothiophene, 2-trinoternyl-1-methyltrifluorovirol-t- can be used. The aldehyde represented by the general formula (III), which is one of the raw materials, is an industrially easily available compound, such as formaldehyde, acetaldehyde, 2-methylpropanal, 2.2
- Using dimethylpropanal, undecanal, benzaldehyde, p-chlorobenzaldehyde, p-methoxybenzaldehyde, phenylacetaldehyde, 2-phenylpropanal, cinnamaldehyde, crotonaldehyde, 2-benzyloxypropanal, 2-acetoxypropanal, etc. be able to. The vinylsilane used can be used in a range from 0.3 molar equivalent to 100%, but does it affect the reaction? For this purpose, it is preferable to use equimolar to 2 molar SR.

The present invention is intended to be carried out in the presence of a fluorine anion source. Sources of fluorine anions include tris(diethylamino)sulfonium difluorosilicate (TASF), )lis(dimethylamino)sulfonium difluorosilicate, tetrabutylammonium fluoride (TBAF), trimethylbenzylammonium fluoride, cenium fluoride, and fluoride. Potassium etc. can be used. The sweetener used is a so-called catalytic lid.

The present invention is preferably carried out in a solvent, such as ether solvents such as diethyl ether, tetrahydrofuran (THF), 1,4-oxane, ethylene glycol dimethyl ether, ethylene glycol dimethyl ether, dimethyl forkamide, etc. , amides such as hexamethylphosphoric acid triamide, urine complexes such as N,N-dimethylpropylene urea, and sulfokids such as dimethylsulfoquinide can be used.

)y-S? ,,11'1-50℃ to 100U, but in order to perform efficiently, the temperature should be -20C to 50C.
is preferred.

The present invention will be explained in more detail with reference to Examples below.

Example 1 PhCHO+Et3SICF=CF2 Benzaldehyde 318 Q (3,00mmol
) TA8F (LM THF solution) in THF4 seedling solution
0.2 IILt) ethylsilyltrifluoroethylene (405 mmol) (2.07 mmol) was added, and the mixture was stirred for 24 hours with a strainer.

After removing the catalyst with a silica gel column,
The P solution was compressed. The obtained crude product is folded into a disposable folding box,
Colorless oil (]-]phenyl 23.3-1・'J fluoro-2-propenyl ox/)) 74
13~? Uta. Yield: 66 cm.

bp knee 100 CI 1mm (Kugel).

Bird + I-NM)t (CDCI 3):
δ 0.5-0.8 (ITh 6H).

0.8-1.1 (m, 'IH), 5.46 (d
dd, J=2Hz+4Hz, 251-1x, IH
), 7-2 to 7.5 (m+ 5H).

"F-N ratio (CDCI, -CFCI 3): δ-10
4(ddd, J=2Hz, 33Hz, 801-1
z.

IF), -120 (ddd, J=4Hz+s.

)1z, 115[-1z, IF), -185(d
dd.

J=25Hz, 33Hz, 115 to 11z, 1F)・
1tL (neat): 2965.2B90.17
92.1308°1260.1112.1100,10
66°1004, 856.840.824.740°6
98crn-”.

Mass Cm/z (%) ); 274 (M
"10i-C, HS+ 11) 273 (M-C2H,,
53), 171 (7).

151 (24), 149 (31), 121 (2
2).

106 (10), 105 (100), 103 (6)
10.1 (12), 87 (6), 7.8 (6)
, 77 (74), 75 (7), 59 (7), 49
(7).

47 (7), 45 (5).

Elemental analysis values: c, 5H2, F, calculated values for osi: C, 59,58; H, 7,00 articles.

Apical value: (,:, 59.46;) -1,6,99%
.

Example 2 C1°H2,CHO+H13SiCF=CF2triethylinyltrifluoroethylene 198"f.

(1,01romol), Undecanal 208
J9 (1,22 mmol) of THk' 2 Ini#
TAsF NM THk' solution in solution 0.1 ml
(0.1 mmol) was added 1 drop and stirred in a drawer for 12 hours. After removing the catalyst with a silica gel column, it was made under reduced pressure. The cut crude product was subjected to layer chromatography (silica gel , methylene chloride/:hexane=1
: 2) to 8 and colorless oily 1.1.2-)lifluoro-3-triethylsiloxy-1-trithecene 21
Obtained 6Iq. Yield 59%.

IH-NMR(CL)CI, ): δ 0
．． 4-0.75 (m, 6l-i).

0.75-1.1 (m, 12)1), 1.27
(s, 16H), 1.4-1.8 (m, 2H),
4.28 (dm.

J=26Hz, IH).

ls-NM)L (CL)CI, -CFCI,)
: δ-104(ddcL J=IHz+33)1z,
53Hz+ IFL-120 (ddd, J=3Hz, 8
3Hz, 114Hz, IF), -187(ddd,
J=26)it.

33Hz, 114Hz, IF)-IR (neat): 2970, 294θ, 1793,
147111308, 1262. 1096. 10
06,750°732crn-'.

M ass [rn/z (%)): 337
(M+-C2H,,15)+225 (18), 211
(24), 183 (19).

145 (10), 117 (10), 115 (22
).

107 (14), 105 (50), 103 (1
6), 95 (11), 87 (98), 83 (1B)
, 81 (15), 77 (49), 75 (40),
73 (15), 69 (26), 67 (13), 59
(23), 57 (26), 55 (39), 47 (
15) + 43 (47), 41 (29), 29 (
17), 28 (21), 18 (32).

7C search analysis value: (, : l, H,, F, O performance, total μL: C, 62, 25; Ratio I U
, 17 Taro・Mitsurii tk: e, 62.
52; H, 10,05%・'-kbI! 11 Tali 3 PhA'el-1 (J + Et 3δ1CF=C
F2 triethylsilyl trifluoroethylene 206tn
y (1,051111nll 1 ), THF2a of cinnamaldehyde 162q (1,23 mm o)
TIP (IMT) lFg liquid) Q, la/ (
0.1 mmol) was added and stirred for 12 hours in a chamber pot.

After removing the catalyst with a sewate column (silica gel),
Vacuum #Compressed. The obtained crude product was subjected to thin layer chromatography (silica gel, methylene chloride:hexane = 1:
1.1.2-) Lifluoro-3-triethylsiloxy-5-phenylmepenta 1
．． 4-Diene 149 was obtained. Yield 43%.

"l-1-NMRl-1-N,): δ0.5-0.8(
Turtle 6H).

0.8~1.1 (m, 8t(), 5.03
(d, m, J=~7.5 (rn, 5)1).

"F-NMR (CDCI, -CFCI,): δ-10
3 (dd, J=31Hz, 79Hz, IF), -119
(ddd, J=4Hz, 79Hz, 115Hz.

IF), -185 (ddd, J=24Hz, 31Hz+
115Hz+IF)・IR(neat):
2970, 2890, 1793.1308°1260
．． 1118.10B0.104? .

1006.802,747.694 Tan-1゜Mas
[m/z (%)): 32B (M”, 2), 30
0 (12), 299 (55), 197 (23).

178 (H)), 17? (75), 175 (
50).

155 (24), 147 (42), 146 (33L
133 (10), 128 (16>.

127 (44), 115 (11), 106 (10)
, 105 (100)? 87 (24).

77 (91), 75 (15), 59 (20).

47 (14)・7c cumulative analysis 4#L: mt for CHHoFsSjO
n ii: C, 62, 17;) 1. 7.0
6% - Actual value: e, 62.22; H, 7,34 chi. Fire axis example 4 Undecanal 170q (1,00 mm, o l),
(T' of -1-triethylsilyl-1,2-difluoroethylene 216q (1-21 mmol)) JP
2nd green onion i11 [TAsF (I M'll'11)'
Bath solution Q, 1 ml, (0.1 mmol)' (1 ljl was lowered with zOc, and stirred with OC for 20 minutes and 24 hours with 24 hours. After removing the catalyst with a silica gel column,
I made a decompression girl. The obtained crude product was subjected to thin layer talomadography (silica gel, methylene chloride:hexacyl=1:
By purification in step 1), a colorless oil (2)-1,2-
) Fluoro-3-t! 162 jv of 7 ethyl 70 quin-1-tridecene were obtained. Yield 47%.

J(-NMle(CDCI,): δ0.4~0.8
(+n+6mu().

0.8-1.1 (m, 12M), 1.27 (
sll 6H), 1.4-1.8 (m, 2H),
4.57 (dm.

J=27Hz, IH), 6-93 (dd, J=5Hz
, 74Hz, 1)1)・"F-Ntvil(CL)CI, -(J"CI,)
:δ-175(ddd, J=6Hz, 27Hz, 1
27Hz.

IF), -180(ddd, J=7Hz, 74Hz.

127)iz, IF).

IR(neat): 2970.2945,2900.
287511033, 1097. 1007,749
．． 732319 (M+-C2i(,,37), 207
<25).

193 (46), 175 (14), 165 (11
), 127 (15), 125 (10), #123
(27), 121 (17), 115 (32).

113 (24), 109 (11), 107 (37
).

105 (86), 103 (12), 99 (26)
.

97 (17), 95 (33), 93 (36).

87 (39), ) 15 (11), 83 (34).

81 (35), 79 (27), 77 (85).

75 (41), 71 (13), 69 (100).

67 (30), 59 (28), 57 (40).

55 (74), 47 (25), 43 (75).

41 (93), 29 (31), 27 (10)
.

1B(26)・61 draws against redundancy analysis Hani 20 Emperor #1mgF2USi,
Value: U, 65.47; l (, 10,99 pieces.

Missing value: e, 65.59; le 11.01%.

Example 5 1-triethylsilyl-1,2-difluoro-1-octene 281'l (1,20mmol), benzaltehyde 106a+? (1,00 mmol) of T
Add TASk” (IM T) iF solution) Q,ld (0.1 mmol) to HF2tnl solution and make 4
Stir for hours. After removing the catalyst using a silica gel silica column, the mixture was condensed under reduced pressure.

The obtained crude product was sheathed by thin layer chromatography (silica gel, methylene chloride:hexane = 1:2),
Colorless oily 1-triethylsiloxy 7°η l-phenyl-2,3-difluoro-2-←1,000 284
■f, I got it. Collection-JA84chi.

IH-NMIL (CDCI3): δ0.47-0.80
(m, 6H).

0.80-1.13 (m, 12H), 1.13
~1.74 (m, 4H), 2.08~2.64 (
m, 2l-1).

5.77 (dd, J=27Hz, 4Hz,
IHn.

7.20-7.48 Cm, 5H).

"F-NM (CDC1, -CFCI,): δ-152
(ddt, J=125Hz+4Hz+22Hz.

IF), -193(ddt, J=125Hz, 27Hz
I 5) (ZI IF) - HL (neat): 2970y 2B90, 1453
．． 1214°1174.1091.1068.1004
,856°745.733,700cm-,'.

MasS [m/z (%)): 312 (M"+1-
KL 10).

311 (M”-Et, 37), 211 (22).

159 (25), 147 (47), 133 (20)
.

117 (93), 115 (26), 105 (87
).

91 (49), 85 (29),? ? (4B).

75 (25), 57 (30), 43 (31).

41 (21).

Elemental analysis value; (-19H30F2 (1st shift calculated against JSl: C, 67,02;) L 8.88%.

Actual value: U, 66.72;? Example 6 1-ethylthio-1,2-difluoro-2-triethylnorylethylene 290 q (1,22 mmo I)
, base/saldehyde l 06 * (1,OOmmo
+)'I'I(I'2rnlh14'1VCTkS
F (IM THF common i) 0.1 +aA(0,1r
[n port 101] was stirred at A1'L and M temperature for 8 hours. After removing the catalyst with a phosphoric gel/II-tocolumn, the product was made into shoes under reduced pressure. The obtained fc crude product was purified by thin layer chromatography (silica gel, methylene chloride:hexane = 1:1) to obtain 1-triethylsiloxy-1-phenyl-2,3-difluoro-3-ethylthio-2 as a colorless oil. -Propene 296- was obtained. Yield 86fD.

'H-NMkL (CDCI,): J O, 47
~0.85 (m, 6H).

0.85-1.14 (m, 9H), 1.27 (
t, J=7Hz, 3H), 2.76 (dq,
J=1)1z, 7Hz, 2H), 5.82 (dd,
J=4Hz+25)(z, 1)ri, 7-16~7
．． 50 (m, 5H).

! '1''-NMRCCDCI, -CFCI
, ) : δ −131(dd.

J==4Hz, 142Hz, IF), -149(dd.

4z, 142Hz, lk') on J-25.

I) L(neat): 2975.2900,125
8.1097゜1070.1008.858,838,
749゜732.701.574σ "1゜MassCm/z (6), l: 345 (M++1
．． 2), 344 (M”, 8), 316 (19), 31
5 (M+-Wt, 79), 283 (52), 213
(20).

183 (20), 151 (97) l 149 (
63).

135 (35), 129 (36), 105 (10
0), 91 (22), 87 (23), 77 (42)
, s9 (20), 29 (39).

Elemental analysis value: CItH2! Calculated for F20SSr! : C,, 59-26;) 1.7.61%.

Actual value: C, 59, 11; Lua, 84 thi Example 7 1-Chloro-1-triethylsilyl-2,2-difluoroethylene 140q, (0,66 mmo5), benzlkf hydro 1'F (0 , 66 mmol) of T
) iF Iaj solution to TASF' (IM i'l
1F solution) 0.06 mj (0.06 mj) was added dropwise and stirred at storm temperature for 12 hours. After removing the atom using a silica gel filter column, the solution was reduced to a concentration of 11 and 4 nm.47-
Purification by chromatography (silica gel, methylene chloride:hexane = 1:2) gave 69IIli of 1-)rieternroxy-1-phenyl-2-10roa,3-difluoro-2-propene as a colorless oil. Yield 38%
.

”)1-NMI-L (CDCI, N: δ
0.47-0.82 (m, 6) 1).

0.82-1.11 (m+9H), 5.04 (
t, J=314z, IH) -7,23~7.50
(m, 5H).

"F-NMK (eL)CI, -CFCI 3):
δ-88 (dd.

J = 3Hz, 45Hz + IF), -92 (dd.

J = 3Hz, 45Hz, IF).

lru(neat): 2975,2900.1
744.12B7゜1093.1060,1014,8
34. 748°730, 703rrn-1°Mas s [m/z (%)'): 291 (M
++2-Et, 30).

290 (M++1-Et, 16), 289 (M+-
Et, 76), 187 (10), 167 (48).

166 (11), 165 (100), 152 (10
).

151 (27), 139 (32), 137 (9
2).

105 (55), 102 (19), 77 (73"
.

75 (11), 59 (12), 47 (10)
.

Elemental analysis: Calculated for C, 5H2, ClF20Si: C, 56,50; H, 6,64%.

Actual value: C, 56,62; H, 6,68%.

Fire 1 Example 8 1-trimethylsilyl-1,2-difluoro-3゜3-
Dimethyl-1-buty7233q (1,21 mmol),
Penzaltehyde 106 alt (1,OOmmo
0.1 aj (0.1 mmol) of rhSF (IM THF solution) was added to 2 ml of THF solution of I), and the mixture was stirred at room temperature for 7 hours. After removing the catalyst using a liquefied gel carbonate column, the mixture was concentrated under reduced pressure. The resulting crude product was purified by thin layer chromatography (silica gel, methylene chloride:hexane; 2) to obtain 1-triethylsiloxy-1-7enyl-2,3-difluoro-4,4- as a colorless oil. /
Methyl-2-pentene 112~ (yield 38%) and
Colorless oily 1-7enyl-2,3-difluoro-4,4
-tumethyl-2-bentenol 108F (yield 48%)
I got it.

Physical properties of 1-triethylsiloxy-1-2-enyl-2,3-difluoro-4,4-dimethyl-2-pentene.

'H-NMR, (CDC1,): δ0.19 (s,
9H), 1.23 (t, J = 2Hz, 9H)
, 5.77 (dd, J=5Hz+26Hz,
IH) -7,16~7.49(rn,5H)S''P-NMIL (C1)CI, -CFCI,
): J-154 (d.

J=123H2IIF), -169(dd, J=26H
z, 123Hz, 1') - IR (neat): 2975.1252,123
4.1120°1090.1066.880,856,
840°749, 708.698cyy+-'.

Mass [m/z (%)): 242 (M++
1-'Bu, 18).

241 (M+-'But 100), 189 (
11).

179 (10), 174 (13), 149 (31
).

143 (10), 129 (11), 117α0).

105 (12), 91 (10), 77 (26),
75' (11), 73 (71), 5
7 (15), 45 (10) I 43 (10), 4
1 (11).

Elemental analysis ``I 6 H24F 20 J value: C, 64, 39;

11111fL: c, 64.29; f-L
8.25%-1-phenyl-2,3-difluoro-
Physical properties of 4,4-dimethyl-2-bentenol '1l-NA414 (L:Ll(J,): δ1.2
5 (dd, J=2Hz.

2Hz, 91 (L 2.66 (broad, IHL
5.73 (del, J=5Hz, 25Hz, I
H).

7.15-7.47 (Kame 5H).

+9) +'-NmR (CIJ CI, -CFCI
,) 2 J-153 (d.

J=1261-1z, IkN), -169(cld
, J=251-1s, 126Hz, IF).

1R (neat): 3380 (broad),
2980.1233°1124.1026,958,7
30,700 cnl-'.

Mas s Cm/z (%) ) 2 227
(M” +1. 3), 226 (M+, 2
2), 169 (74), 143 (25).

138 (100), 109 (39), 107 (62
), 105 (59), 91 (29), 79 (59)
, 78 (36), 77 (64), 59 (43), 5
7 (70), 51 (30), 41 (27) l 3
9 (20), 1B (86)・Elemental analysis value'C
: Calculated value for rsHrsFzO: C, 69,01
;i(,7,13%・Actual value: C, 6B, 73;H,
7,28%.

Example 9 PhCH(J + Ph+Me 2SiCF=
CF2 dimethylphenyl trifluoroethylene 2
62W (1,21mmol), benzaldehyde 1
071 (1,01 mm61) of THF 2 ml (
(9 liquid KTASF (IMTHF solution) 0.1#I
t and stirred for 65 hours to obtain the desired 1
-dimethylphenylsiloxy-1-7enyl2.3.
3-) IJ fluoro-2-propene was obtained. Following the steps shown in 1 below, dimethylphenyl & was removed and the product was identified. IM hydrochloric acid methanol solution (l-) was added to the reaction mixture, and after stirring at room temperature for 0.5 hours, the catalyst was removed with a silica gel silica column, and the pressure was reduced to 117! did. The obtained crude product W was purified by thin layer chromatography (silica gel, methylene chloride; hexane = 1:2) to obtain colorless oily 1.
-Phenyl-2,3,3-trifluoro-2-brobenyl alcohol 11sjv't''. Yield 61%.

1-7 enyl-2.3.3-trifluoro-2-propenyl alcohol (i 1 m(-NMR(CDC1s): d 2.50 (
broad, IH).

5.46 (ddd, J=l)iz, 4Hz, 2
5Hz.

IH) t 7.2-7.6 (m, 5M>.

"k'-NMR(C1)C1rCFC!, ):
J-102 (ddd.

J=IH2, 32Hz+76Hz, IF) 1-119
(ddd, J=3Hz, 76Hz, 115Hz, I
F), -187(ddd, J=25Hz.

32Hz, 115Hz, IF).

IR(neat): 3350.1790.130B,
1253°1090.1074.1032,1016.
=833.735,698c+n-'.

Mass (m/z (%)): 18B CM”+
35; + 151 (22), 138 (28), 13
7 (100).

109 (43), 79 (27), 78 (25).

77 (35), 51 (2g) - Fire jL+? 1l10 1'heHO+Ph, MesicF=cF.

Methyldiphenylsilyltrifluoroethylene 3335
9 (1,20 mmo 1 ), benzaldehyde 10
TASF (IMTHF solution) o and 1aZt were added to a THF2ILt solution of 6q (1,00 mmo I), and the mixture was stirred at room temperature for 24 hours. Hereinafter, by the same operation as in Example 9, 1-phenylated-2,3,3-) IJ fluoro-2-
79q' of 7'ropenyl alcohol was obtained. Yield: 42 cm.

', A flow side 1I PhC:Do +lt3SiCF=CF', --
Mitriethylsilyltrifluoroethylene 2301'
f (1,17m1nOl), benzaldehyde 1
01 (1,00 mmol) in THF2z4 solution
F (IM'l''HP bath)Q, ld was added and stirred at mold temperature for 5 hours.

TBAI'' (IM T) iF bath solution 0.1+Jl additional force was added and stirred for 0.5 hour at the lowest temperature.Silica gel solution 1
The catalyst was removed using a column, and the pressure was then reduced to a4.

The obtained living bottom matter was annihilated by thin layer chromatography (7 liquefied gel, methylene chloride:hexane = 1:2),
K folk color 7 mountain-shaped (1-phenyl-2,3,3-trifluoro-2-propenyloxy) trifluoro/126~
is a samurai. Yield: 42 buns.

Example 12 r.

Benzaldehyde 111~(1,05mmo I), trimethylsilylpentafluorobenzene 286 #lF
(1,19 mmol) of TASF in 2m solution of THF.
(IM-cho BF l@Q) 0.1 d (0.1mm
ol) t OCT: Drop and soak in OC for 20 minutes 1
The desired 1-pentafluorophenylpendyloquine trimethylsilane was obtained by stirring for 2 hours. The p-trimethylsilyl group shown below was removed and the product was identified.

Add 1 ml of 1M hydrochloric acid methanol solution to the reaction mixture,
The mixture was stirred at the mold temperature for 1 hour, the catalyst was removed using a silica gel sheet column, and the mixture was placed under reduced pressure. By thin layer chromatography (silica gel, methylene chloride:hexane=l:1), 1-pentafluorophyl alcohol c' white Ma249 cape was obtained. Yield 87%
.

Physical property values of 1-pentafluorophenyl be/cyl alcohol mp: 490 1n-NMa (CL)C1, ) : δ3.20 (
broacL IHL6.13 (broad+ IH
) + 7.2~7.4 (rn.

5H).

19F-NMR (CDCI, -CFCI,): δ-14
2 (m.

2F), -154 (m, IF), -161 (mI2
F)・IR(KBr): 3400,1528.1508.1
127°996.950,706.648m-”-n4
assjn+/z (%) ): 275
(M"+t+ 7), 274 (1~1+, 5
1), 273 (6), 23f (10).

197 (12), 195 (3B), 167 (8
).

107 (20), 105 (11), '80 (7)
.

79 (100), 7B (26), 77 (30)
.

51 (16), 50 (6), 39 (5), 29
(12)・Elemental analysis value: (:,,61 calculation 11 for H?FsO
Ward: U, 56.95;) i, 2.57 chi.

2 C, 56, 75;) L 2.5
4%.

Example 13 Undecana-k 16'7'9 (0,982 mmo
l) ,) Rimeter/lilbentafluoropense/2
89W (1,20mmol) °1'HF2aJ#Q
'l'AsF (I M THFmW) 0. To u
(0.1 mmol) was removed with OC and 2
0 minutes, rM4? for 12 hours at room temperature. 1- by
Pentafluorophyl undecyl quinetrimethyl/
Attended Ran. Below, by the same operation as in 12, 1-
White crystals of pentafluorophenylcundecanol 21
0my (yield: 63%) was obtained, and 1J steps were performed.

Physical property value of 1-pentafluorophenylcundecanol mp: 28C'H-NMI ((CL)CI, ): δ0.87 (
broad t, J=6Hz, 3)1), 125
(broad s, 16H).

1.4~2.1 (m+28) + 2.1~2. J
(broa41)1) 5.00 (R])l)・"F-NMR(C1)CI ,-(,'l'(,'l
, ): 0-143 (Tsuru 2F), -155 (m, 1
)'), -162 (m.

2F).

11 ((KHr): 3400.2940.2870,
1526°150? , 1133, 1118; 994
゜979 pieces - 1゜Mass [m/z (%)): 338 (M+, tr
ace).

Ices (8), t97 (1oO), 194 (
6).

57 (12), 55 (9), 43 (24), 41
(15), 29 (10), 18 (5).

Month: #Analysis i1su'Cl7H23"5'i for J
1 praise, 11η: C, 60, 35;) L 6.85%.

Actual value: C, 60,43; l (,6,82%.

Example 14 One pennzaltehyde 106 q (1,00 mmo I
), 1-drimethylsilyl-2.3.5.6-tetrafluorobenzene 266'9 (1,20mmo J)
TI (TASF (IMT) iF solution in 2m F solution) 0.1 trt (0.1 mmol) was added with OC and further stirred with OC for 12 hours to obtain the desired 1
- (2,3,5,6-tetrafluorophenyl)benzyloxytrimethylsilane was obtained. Below, Example 12
By the same operation as above, a colorless oily 1-(2,3,5,
6-tetrafluorophenyl)benzyl alcohol 10
9■ (yield 843%) and performed the same redundancy.

Physical properties of 1-(2,3,5,6-tetrafluorophene;l)benzyl alcohol"?I-NMkL (CDCI,): δ 2
．． 88 (broad+ 18)*6.21 (b
road, IH) 16.94 (t t, J=7
Hz, 10Hz, 11L), 7.2”-7,5(
rn.

5H).

"i'-NMI also (CDCI, -CFCI s): δ-
138 (m.

2F), -143(m, 2F).

117 (nelt): 34001 150B, 125
3n 1097°932.710m.

Mass (tn/z (%)): 257 (M++
1.10), 25G (M+, 63) I 255 (8)
, 238(5).

237 (8), 219 (11), 197 (9).

179 (10), 177 (40)l 149 (
10).

107 (28), 105 (14), 99 (6).

81 (5), 80 (7), 79 (100), 78
(27), 77 (33), 51 (17), 5
0 (6), 39 (5), 29 (10), 1B (5
)・Elemental analysis value: C,,1-[,Calculated value for F2O: e, 60.95;)L 3.1596-Actual value: C,60,75;)l, 3.10 Chi・Fire Stream side 15 r undecanal 170'II (1,OOmmol)
, l-trimethylsilyl-2,3,5,6-tetrafluorobenze 7266 'l? (1,20 mmol) of THF 2trl bath solution LTASF (IM TH
F solution) 0.1 ant (0.1 mmo
l) with OC! ! ! The desired 1-(2,
1-(2,3,5,6-tetrafluorophenyl)undecanol was obtained by the same procedure as in Example 12. White crystal 142 ~ (collection vehicle 44
%) and performed a quadrupedal test.

Physical properties of 1-(2,3,5,6-tetrafluorophenyl)undecanal mp: 50-51C'H-NM)L (CDCI, ): δG, 88 (bro
ad tt J=614z*3H) + 1.27
(broad 51161'()+1.5~2.2 (
nl+ 2HL 2.3 (broad.

IH), 5.03 (broad, 11(), 6.
97 (t t.

J = 8Hz + IOH'Z, IH) - +9? '-NMI-L(C1)CI 3-CFCI 3
): δ-138 (m.

2F), -143(m, 2F)・11t(KBr): 3430,2935.2870.
150&.

1253.1172,912,846 Tan-1゜Mass
(m/z (%)): 320 (M”, 1.2),
18° (10), 179 (100), 176 (8)
.

75 (6), 71 (6), 69 (5), 5
7 (15L 55 (10), 43 (25), 41 (1
5), 29 (10)・Elemental analysis value '01? Calculated value for H24F40:
C463, 73; Lua, 55 outside! 6110K 2 e,
63.65;)L 7.67%.

Example 16 Benzaldehyde 106 H7 (1,00 mmol),
1-drimethylsilyl-4-butyltetrafluorobenzene 340'9 (1,22 mmo 1) in THF
Add 0.1 TASF (IM T)iF bath solution to 2d solution.
The desired 1-(4-)<tyltetrafluorophenyl)lbenzyloxytrimethylsilane was obtained by dropping the mixture under dt-pressure and stirring for 8 hours. Below, Example 1
279qC (yield: 89%) of 1-(4-butyltetrafluorophenyl)benzyl alcohol as a colorless oil was obtained by the same operation as in λ and identified.

1-(4-Butyltetrafluorophenyl)-benzyl alcohol 0 Physical property value 'H-NMI ((CL)CI, ): δ 0.
93 (t, J=7Hz, 3H), 1.1~
1.8 (rn, 4H), 2.69 (t.

J=7Hz, 2H), 2.98 (d, J=8)
1z.

IH) e 6.17 (d, J=8Hz+IH)
, 7.13-7.50 (m, 5H)・19F-NM)L (CL)CI, -CFCI 3)
: δ-145 (S.

4F).

IR (neat): 3390 (broad)+
2975.1489°128 (b 976.702-6
40.

Ma s s (m/z (%)): 313 (M
++1.11), 312) l”, 60) 311
(11), 235 (18), 233 (30), 10
7 (27), = 1105 (36), 79 (100
), 78 (59).

77 (24), 43 (32), 41 (14)+2
7(11).

Elemental analysis value: Calculated value for C17H16F40:
Q 65.38;) L 5.16%.

Actual value: C, 65.12; 5.31%.

Example 17 Pe/Zua Hetehi l゛l 07 my (1,Q l+n
mo I), 1-trimethylnoryl-3,5-one chlorotrifluorohene:y ce/328#I& (1,20
mm0 of 'I'I (TASF (1M
THF solution) 0.05ml (0.05mmol)
The desired 1-(3,5-dichlorotrifluorophenyl)be/
Diluoquintrimethyl 7 runs were obtained. Hereinafter, 1-(3,5-cyclotrifluorophenyl)benzyl alcohol 2 with a poor appearance and poor color was prepared by the same operation as in Example 1.
71q (yield 87%) was obtained and identified.

1-(3,5-dichlorotriflumerophenyl)benzyl alcohol o Physical property value 'H-NMIL(CI)CIS): δ2.80 (
broad d, J=6Hz+IH) v 6.1
8 (broad 4 J=6Hz, IH), 7.32
(5,5H)-1R(neat), : 3360.1
612.1449,1210゜1190.1092,1
066.1040°1025.788,727,697
,593crn-'Mass Cm/z (%):
] 308 (M++2.19), 307 (M++L
7) I 306 (M+, 29).

229 (19), 227 (17), 107 (27
).

105 (13), 79 (100), 78 (34)
.

77 (26), 51 (14).

Elemental analysis doctor: n' for C, 3H, C12F, O
A Toy-L: C, 50, 84;) (, 2, 30
A pun.

Actual value: U, 50.70; H, 2,27%.

implementation ? ! 118 Benzalnahyde 53 q (0,50mm0 l),
) Limethylsilylbe7tachlorobenzene 192'F (g
, 60nunol) in THF 1rLt solution 1c
TA8F (LM'1"HF Swamp a) 0.05d (0,0
The desired 1-pentachlorophenylbenzyloxytrimethylsilane (i-) was obtained by adding 5 mmol) f dropwise and stirring for 3 hours with a blood feed. White 1-pentachlorophenyl was obtained by the same procedure as in Example 12 below. Benzylal''-7'142'f (yield 80%>tm, I
01-Pentachlorophenylbenzyl alcohol subjected to I-J determination "H-ry Ma <<: Dcs,> 2 δ
3.46 (broad d, J=10Hz
, 1M), 6.67 (broad d, J=1
0Hz+IH)+7.1~7.4(m+5
)1).

IK (KBr): 3200-3600 (broad
), 135 & 111g, 1042, 1026, 727,
693°656.552.

+vla s S [rn/z (%)):
358 <M'″+4.20).

35 mo (ni'+2. 32), 35 noon (M", z
O), ytq<q3).

107 CE) 8), 7’? (100).

78 (3B), Wa'7 (36).

Redundancy analysis middle: C,31(,C1,for u!i'
J4-1 Straight 2 C, 43, 80;) L 1. 'll
B%-Ouyuri(,,1: C,43,'71; t
-L IJf-96゜/Lj about゛Applicant-f' Continued Amendment Satoshi (spontaneous) June 18, 1985/1. '＋＃'lL'＋Director Shiga Gakudono J, 11+
4'l's I': 1981 Kantoku Y'r Application No. 142450 2, Name of the invention Process for producing halogen-substituted ethylene derivatives 3, Detailed description of the invention in the supplementary specification 1 ” column 5, content of amendment 1) “Octene” on page 21, line 7 of the specification of the present application is corrected to “hexene.”

2) Correct to "Decanal Jtr Decal" in line 441i'4.

that's all

Claims (1)

[Scope of Claims] In the presence of a source of fluorine anions, a vinylsilane represented by the general formula ▲ has numerical formulas, chemical formulas, tables, etc. ▼ and an aldehyde represented by the general formula RCHO are reacted,
Method for producing halogen-substituted ethylene derivatives represented by the general formula ▲Mathematical formulas, chemical formulas, tables, etc.▼
In the formula, R is an alkyl group, an aryl group, an aralkyl group, an alkenyl group, or a hydrogen atom; R^1, R^2, and R^3 are a halogen atom, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, It is an acyloxy group, an alkoxy group, an amino group, a thio group, a cyano group, or an alkoxycarbonyl group, and R^1 and R^3 together with the bonded carbon can form an aromatic ring. R^1, R^
2. At least one of R^3 is a halogen atom. R^4, R^5, R^6 are alkyl groups, aryl groups,
It is an aralkyl group or an alkenyl group. ).