JPS61246138A - Production of fluorinated allyl derivative - Google Patents

Abstract

PURPOSE:The title substance is obtained by reaction of ethyl 2-(1-hydroxy-2- chloro-3,3-difluoro-2-prpenyl)-3,3-dimethylc-yclopropanecarboxylate with a halogenation or sulfonation agent. CONSTITUTION:The reaction of an alcohol of formula I (R is alkyl, aryl, alkenyl, H; Y is halogen; X' is halogen, alkoxy, amino, thio, alkyl, H) with a halogenating reagent such as diethylaminosulfur trifluoride or a sulfonating reagent such as methanesulfonyl chloride is carried out, when necessary, in the presence of a base such as pyridine at -78-50 deg.C to give a compound of formula II (Y is halogen, sulfonyloxy). USE:A starting material of chrysanthemumic acid bearing a fluorinated allyl fragment which is used as a synthetic intermediate of pyrethroid insecticides.

Description

[Detailed description of the invention] [Industrial application field] The present invention is based on the general formula % () (wherein, 几 is an alkyl group, an aryl group, an alkenyl group, or a hydrogen atom, X is a halogen atom, and f is a) 10 gun atoms,
It is an alcohol group, an amino group, a thio group, an alkyl group, or a hydrogen atom, and Y is an I-logon atom or a sulfonyl group. ).

The compound represented by the general formula (I) produced by the method of the present invention is useful, for example, as a synthetic intermediate for highly active fluorine-containing analogues of pyrethroid insecticides.
Chrysanthemum acid derivatives having an allyl heptadate moiety, such as 2-chloro-3,3,3-)lifluoro-1-propenyl)-3,3-')l-methylcyclopropanecarboxylic acid ester (JP-A-53-95945 , 54-112820.54-13
0537.55-59141.55-89248.55
-111488)).

[Conventional technology]

Conventional 2-(2-chloro-3,3,3-trifluoro-1
-propenyl)-3,3-dimethylcyclopropanecarboxylic acid ester, etc., as a method for synthesizing chrysanthemum acid derivatives having an allyl heptafluoride moiety: (i) ethyl 3゜3-dimethyl-4-pentenoate is converted to polyhaloheptafluoride; A method of adding ethane followed by cyclization and dehydrohalogenation (JP-A-53-9
5945), (1 plate) Method of adding diazoacetic ester to 1-polyfluoromethyl-1-chloro-4-methyl-1,3-pentadiene (JP-A-53-95945)
, (iii) 2-(2,2-dichloro-2-polyfluoromethylethyl)-2-chloro-a,a-dimethyl-cyclobutanone method utilizing ring reduction reaction (JP-A-56-92830) It has been known. However, although method (i) is effective for the synthesis of limited chrysanthemum acid derivatives, it is often difficult to obtain polyhalofluoroethane as a raw material. Methods (ii) and (iii) both have drawbacks such as complicated synthesis of raw materials and difficulty in industrial implementation.

[Object of the Invention] As a result of intensive studies by the present inventors on a method for industrially synthesizing a chrysanthemum acid derivative having an allyl fluoride moiety by overcoming the drawbacks of the conventional methods, the inventors found that the general formula (1) The present inventors discovered a method for efficiently producing olefins having a polyhalomethyl group represented by the formula, and completed the present invention.

[Structure of the invention]

The present invention is based on the general formula (wherein, 几 is an alkyl group, an aryl group, an alkenyl group, or a hydrogen atom, X is a halogen atom, X' is a halogen atom,
It is an alkoxyl group, an amino group, a thio group, an alkyl group, or a hydrogen atom. This is a method for producing an allyl heptatonide derivative represented by the general formula tI), which comprises reacting an alcohol represented by the following formula with a halogenating agent or a sulfonylating agent.

A method of acid hydrolyzing an aldehyde adduct of an alcohol hapolyhalovinylsilane represented by the general formula (It), which is a raw material of the present invention (see reference side below), or an aldehyde addition reaction of trifluorovinyllithium (J ,
F. Normant et al.

5ynthesis, 1975, 122; P, Tarr
ant et al.

J, Org, Chem, Dish, 839 (1963))
K can be easily manufactured. Examples of these alcohols include ethyl 2-(1-hydroxy-2-chloro-3,3-difluoro-2-propenyl)-3,3-dimethylcyclopropanecarboxylate, 2-(1-hydroxy-2-chloro-3,3-difluoro-2-propenyl)-3,3-dimethylcyclopropanecarboxylate; (3-phenoxyphenyl)methyl chloro3,3-difluoro-2-propenyl)-3,3-dimethylcyclopropanecarboxylate, 2-(1-hydroxy-2-chlorocz-3,3-9fluoro-2- Cyano(3-phenoxyphenyl)methyl propenylcyclopropanecarboxylate, 2-(1-hydro-2-chloro-3.a-diyl-2-propenyl)-3,3-dimethylcyclopropanecarboxylate pentafluorophenylmethyl , ethyl 2-(1-hydroxy-2,3,3-1lifluoro-2-propenyl)-3,3-dimethylcyclopropanecarboxylate, 2.3.3-trifluoroallyl alcohol, 3,4.4- Trifluoro-3-buten-2-ol, 1,1.2-1-lifluoro-1-tridecen-3-ol, 1.], ]2-4lifluoro-4-methyl-1-penten-3-ol, 1. 1.2-trifluora-5-7x2h-1.

3-chloro-4,4-difluoro-1-butene-3
-ol, 1,1-difluoro-2-chloro-2-chloro-3,3-diyfluoro-ol, 2-(1-human0-V-cy2,3-difluoro-2- propenyl)
-ethyl 3,3-dimethylcyclopropanecarboxylate,
Ethyl 2-(1-hydro-2,3-difluoro-2-butenyl)-3-dimethylcyclopropanecarboxylate, 2-(l-hydroxy-2,3-difluoro-2)
Ethyl-3,3-dimethylcyclopropanecarboxylic acid ethyl, 2-(]-]hydro-2,3-fluoro3-methylthio-2-propenyl)-3,3-dimethylcyclopropanecarboxylate, 2-(1-human cx)2,3-difluoro Ethyl -3-cyano-2-propenyl)-3,3-dimethylcyclopropanecarboxylate, 2-(1-hydrocyano-2,3-difluoro-3-dimethylamino-2-propenyl)-3,3-dimethyl Ethyl cyclopropanecarboxylate and the like can be used. The other raw materials, a halogenating agent and a sulfonylating agent, are easily available industrially. Examples of the halogenating agent include diethylaminosulfur trisulfur tri7tide (DA8T), phenyl sulfur trisulfide, sulfur tetrafluoride, hydrohydrocytic acid, pyridine-hydrofluoride, 1゜1.2.2- Tet2fluoroethyldiethylamine, 2
-fluorinating agents such as chloro-1,14, -trifluoroether diethylamine, selenium tetrafluoride, trifluorodiphenylphosphorane, difluorotriphenylphosphorane, and fluoropropene-diethylamine;
Thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxybromide, carbon tetrachloride-triphenylphosphine, carbon tetrachloride-trifioctylphosphine, carbon tetrachloride-t! J Etherphosphite, diphenyltrichlorophosphorane, triphenyldichlorophosphorane, diethyl≠(
chlorinating agents such as 1,2,2-)dichlorovinyl)amine,
Brominating agents such as thionyl bromide, phosphorus tribromide, phosphorus pentabromide, phosphorus oxybromide, carbon tetrabromide-triphenylphosphine, diphenyltribromophosphorane, triphenyldibromophosphorane, etc. are used, As the sulfonylating agent, sulfonylating agents such as methane sulfo chloride 1 chloride 1) -) trifluoromethanesulfo chloride 11 chloride benzene fluoromethanesulfone ill, N-methanesulfonylimidazole, N-trifluoromethanesulfonylimidazole, etc. can be used. can. The halogenating agent or sulfonylating agent to be used can be used in an equimolar amount to a large excess relative to the substrate, but in order to carry out the reaction efficiently, it is preferably used in an equimolar to 2 molar equivalent amount.

The present invention is preferably carried out in the presence of a base if necessary, and examples of the base include amines such as pyridine, p-dimethylaminopyridine, triethylamine, and diisopropylethylamine, sodium hydride, calcium hydride, potassium hydride, etc. metal hydrides can be used. The amount of base used can range from an equimolar amount to a large excess relative to the substrate, but in order to carry out the reaction efficiently, it is preferable to use an equimolar to 2 molar equivalent amount.

The present invention can be carried out without a solvent or in a solvent, and examples of the solvent include diethyl ether, tetrahydro7ran, 1,4-dioxa and ethylene glycol dimethyl ether, 1 dichloromethane, chloroform, carbon tetrachloride, tetrachloroethylene, etc. , halogenated hydrocarbon solvents such as trichloroethylene, hydrocarbon solvents such as hexane, pentane, cyclohexane, benzene, toluene, and amides such as dimethylformamide and hexamethylphosphoric triamide.

The reaction proceeds at a temperature of -100°C to 150°C, but preferably -78°C to 50°C for efficient performance.

Hereinafter, the present invention will be explained in more detail with reference to Reference Examples and Examples.

Example 1 Ethyl 2-(1-hydroxy-2-chloro-3,3-difluoro-2-propenyl)-3,3-dimethylcyclopropanecarboxylate 10.3 ■ (3,83 x 10 m
After cooling a 2 m solution of 1 mol) of dioxic aa meth y O to -50°C, 0.006 m/ml of DA8T was added and the temperature was slowly raised to room temperature. ``As observed by F-NMR, the disappearance of the raw material was not complete, so it was cooled again to -50℃ and DA8￥0.
．． 002 i was added. After raising the temperature to room temperature, the reaction solution was purified with thin layer Chromadog 2F (silica gel, dichloromethane) to obtain colorless oily 2-(2-chloro-3,
Ethyl 3,3-)lifluoro-1-propenyl)-3,3-dimethylcyclopropanecarboxylate 6.8 IH9
I got it. Yield: 66 cm.

'H-NMR (CL) C13): δ1,2-1.4
(m, 9H).

1.6-1.7 (m, IH), 4-2. s
(m, IH), 14, U-4,3(m, 2H)
, 6.0-6.2 (m, IH) 1 Sei-NMR (
C1) C13-CFCl2): δ-69(s, 3H)
IR (neat): 1733, 1724, 1304, 1
286°1228.11?6,1144α −+ Mass (m/z (%)): 270 (M, 1), 2
25(18).

199(24), 197(68), 161(20).

1410 薯), 41 (18), ・29 (100) + High Miss: C1, H14F5C102 (M
), the calculated value is 270.0632. Actual value, 27
0.0632 Example 2 2-(l-hydro or co-2-chloro-3,3-Schiff /
l', t O-2-propenyl)-3,3-dimethylcyclopropanecarboxylic acid ethyl 6.211Igω, 0
Add pyridine U, 004 id, 0.1 thionyl chloride to a solution of 23 mmol 1 edel ether at -50°C.
01) 4117 was added, the temperature was raised to room temperature, and the mixture was left for a while. Purification by thin layer chromatography (silica gel, dichloromethane) yielded 2-(2,3) as a colorless oil.
-dichloro-3,3-difluoro-1-7'ropenyl)
3. Ethyl 3-dimethylcyclopropanecarboxylate 5,
011g was obtained. Yield 75%.

'H-NMR: δ 1.1-1.4 (m, 9H),
1.75 (d, IH).

2.40 (dd, IH), 4.2 (q, 2H
), 6.13 (d, IH) 19F-NMR (CDCl2-CFCl2): δ-54
(s, 2F) + Mass (m/z (%)): 286 (M, trace
), 241 (10), 215 (25), 213 (37)
, 177(12), 141(17), ? ? (10), 6
] (15).

41 (17), 39 (15), 29 (IOL+), 27
+ High Mass: CC11H14F2C1202
Calculated value for (): 286.033B, actual value 228
6.0358 Example 3 2-(1-hydroxy-2,3,3-trifluoro-2
-propenyl)-ethyl 3,3-dimethylcyclopropanecarboxylate 9.6 tag (0,038mmol)
DAST in dichloromethane 0.5m/@ solution at -50℃
Ooo 06- was added and the temperature was raised to room temperature. The reaction solution was purified by thin layer chromatography (Curicataru, dichloromethane) to obtain 2-(2゜3.3.3-) as a colorless oil.
7.8119 of ethyl tetrafluoro-1-propenyl)-3,3-9methylcyclopropanecarboxylate was obtained.

Collection EE81S6 (d, If (), 2-30 (dd, IH
), 4.1s (q.

2) 1), 5.30 (dd, IH) 19F-NMR (eDcl 3-CFC13): δ-
72,8 (d, 3F).

−136,9 (dq, IF) + Ma s s (m/z (%)): 254 (M,
3), 209 (24), 182 (10), 181 (92
), 141(18), 115(11), 97(12),
? ? (11), 59(10), 47(21), 4](2
]).

39 (15), 29 (100), 27 (17) + High Mass: C1, H14F402 (M)
Calculated value for K: 254,0929. Actual value: 25
4. L)936 Example 4 2-(1-hydroxy-2,3,3-trifluoro-2
-Probel)-3,3-dimethylcyclopropanecarboxylate (cis-trans mixture) l 044
(0,4] 3mmo, l ), pyridiyo, osm (
Add 0.6 mmol of thionyl chloride to 1 ml of diethyl ether pv solution at -78°C. υ5d was added and the temperature was raised to room temperature. After standing for about 5 minutes, the reaction solution was directly subjected to thin layer chromatography (silica gel, dichloromethane).
L, colorless oily 2-(2,3,3-)lifluoro-3-
Ethyl cxa-1-propenyl)-3,3-dimethylcyclopropanecarboxylate 969 was obtained. Yield: 486 cm.

'H-NM (cDet 3) (Spectrum of cis-trans mixture) For cis form: δ 1.21 (s, 3H).

1.27(t, 3H), ], 3](s, 3H), 1.6
7 (d, IH), 2.30 (ddd, 1) 1), 4.1
8(q of ABq, 2)1), 5.26(dd,
IH) Two δ 1.27 (s, 6H
).

1.27 (t, 3H), 1.89 (dJ = Tan Tsujiguchi IH
), 2. J 1 (dd@]H), 4j 8 (q o
f chain, 2) 1), 6.10 (da, If()1?F-
NM几(CDCl2-CFCI,) Spectrum of nitrogen-sutrans mixture δ-58,5(d.

2F), -58,8 (d, 2F), -t31 (dt.

IF), -1a3(dt, IF) IR(neat): 1733, l 221.1
, 190, 115 courtesy 113β.

1091.1062. ]050,934CI & this ss(
m/z (%)): 270 (M, 3), 225 (17
).

199(19), 197(58), 162(11).

16] (34), 34] (20), 97 (13), 65
(15), 59 (10), 41 (19), 39 (17)
.

29(IL)0), 27(2L)) High Mass: C,,H,4F3CIO2(M
) calculated value: 270. υ633. Actual value: 27u
, 0643 Example 5 n-C1. )(21CH=C(CI)CF3DAST
1,1-difluoro-2-
Chloro-1-tridecen-3-ol 27~(t), l
Ommol) was added and the temperature was raised to room temperature. After concentration under reduced pressure, 1. J, 19 1-trifluoro-2-chloro-2-tridecene was obtained. Yield: 70 cm.

'H-NMR (CDC1,): δ0,7-1. L)
(m, 3H).

2.27 (s, ]6H), 2.1-2.4 (m, 2H)
.

6.43 (tq, IH) "F-NMR (CDCI, -CFCI3): δ-69
(m, 3F)■几(neat):2940,2865.
130? , 1186゜1]48csz' + Massrm/z(9G)):27υ(M, tr
ace), 1] 1(10), 98(12), 9
7(18), 85(14).

84 (28), 83 (25), 71 (32), 70 (3
2), 70 (64), 69 (56), 57 (77).

56 (97), 55 (55), 43 (100), 42 (
25), 41(66), 39(13), 29(36).

Elemental analysis value: Calculated value for C13H2□ClF3:
C, 57, 67; H, 8, 19% Actual value: C, 57,
95; H, 8, 17th Example 6 n-C,. H2,CH=C(CI)CF2C11,1
-Difluoro-2-chloro-1-tridecen-3-ol 26 ml (0,097 mtnol) with pyridine 0
．． 0.2m (0.25 mmol) and thiol chloride (0.01R/(0.14 mmol)) were added thereto, and the mixture was stirred at room temperature for 2 hours. Purification by thin layer chromatography (silica gel, hexane-dichloromethane 4:1) gave 1,1-difluoro-1,2-dichloro-2-to-IJdecene 7. Yield 61%.

'H-NMR (CL) C1,5): δ0,7-1.0
・(m, 3H).

1.26 (broad s, ] 6H), 2.
1-2.4 (m.

2H), 6.40 (t, IH)"F-NMR
(CL) C1, -CFCI, ): δ-53(s, 2F
) + Ma s s (m/ z (%)) 2286 (M
,]), 97(13).

85 (10), 84 (19), 83 (19), 71 (2
2), 70 (43), 69 (36), 57 (55)
.

56 (61), 55 (,39), 43 (100), 42
(17), 41 (54), 39 (14), 29 (35)
.

+ High Mass: C1, H22C12F2 (M
), the calculated value is 286.1037. Actual value: 28
6,1051 Example 7 n-c. H21a(=c(F)cF3DA8T82M
9 (0.5 Gmmol) of diku aH methane 51n! In the solution 'l, ], 2-) 7 to oc1-1-trideceno3
-all l 234 (0,4-tmmol) -7
The mixture was added dropwise at 8°C, and the temperature was slowly raised to room temperature. After concentrating the reaction solution under reduced pressure, it was subjected to thin layer chromatography (silica gel,
Dichloromethane-hexane (1:9) was used for 111 meals to obtain 12 mg of Jl,l,],]2-teto2fluoro-2-tridecene]. Yield 9o%.

'HNMR (C-DC-1s) 2a 0-8-1
−0 (rn −3H).

1.1-1.6 (m, ] 6H), 2.1-2
．． 4 (m, 2H).

1471J, 1362. IJ94. l]4J]050α
-1+ Mass (m/z (%)) 2254 (M, tra
ce), 97(12), 85(12), 84(16),
83(15).

7] (23), 70 (31), 69 (30), 57 (5
4), 56 (47), 55 (34), 43 (100).

42(16), 41(46) + Higtt Mass: Calculated value for C15H2□F4(M)K: 254,1656. Actual value: 254,
1647 Example 8 n-C1oH2, CH=C(F)CF2C11,1,2
-Trifluoro-1-tridecen-3-ol 1261
1 g (0,500 mmo 1 ) c7) di, 111-
f Le! -Chill IWLtfI solution with viridiy O,08
1 m (1, Ommol), thiol chloride 0.038
#E/(0.50 rnmol) was added dropwise and stirred at room temperature for 3 hours. The precipitated inorganic salt was filtered off and concentrated under reduced pressure to obtain a crude product. By making one with thin layer Chromadog 2F (silica gel, hexane-dichloromethane 5:l),
1-chloro-1,1,2-trifluoro-2 as colorless oil
-Tridecene 115μ was obtained. Yield 85%.

'H-NMkL (CDCI): δ0.7-1.0(
m, 3H), 1.1-1.6 (m, ] 5H)
, 2.0-2.4 (m, 2H).

5.47 (dt, 1l-1) 1? F-NMR (CDCl3-CFCI,): δ
-59 (dt.

2F), -131(dtt, IF)IR(neat
):2940,2870,1470,7146°305
2.928m Example 9 C1゜H2, CH=C(F)OF20802Me1.1
．． 2-) Refluoro-1-tridecen-3-oh #1
30111g (0,516mmol) of pyridine 0.2
Methanesulfonyl chloride 0.077aj at mamVcO℃
(1.0 mmol was added dropwise and stirred at the same fA degree) for 2 hours.

After adding water 3 and extracting with diethyl ether (5d×3 times), the extract was dried over anhydrous magnesium sulfate.

After removing the desiccant by filtration, it was concentrated under reduced pressure and then subjected to thin layer chromatography (Nrikaglu, dichloromethane:hexane=l:I).
And n#! By doing this, a colorless oily methanesulfone 1,1,2-)lifluoro-2-tridecenyl 102
I got it. Yield 60%.

'H-NMR, (CDCI 3): δ0.75-1.
05 (m, 3H).

1.1-1.6 (m, 15H), 2.0-2.4
(m, 2H).

3.24 (s, 3 yen, 5.54 (dt, t = Tsurutsu H-shear.

IH) "F-NMR (eDc13-CFCl2): δ-73 (
dt, 2F).

-1as(att, 1p) IR(neat):2935,2870,1392,1
208°1079.966.776α + r&ss (m/z (%)) : 234 (M
-Me802H, 2).

]44(11), 33υ(13), Jυ8(24).

97 (1υ), 85 (ILI), 84 (11), 83 (
15), 79(23), 7](23), ? Q26).

69 (34), 1 (10), 67 (11), 56 (64
), 56 (46), 55 (58), 43 (100).

42 (18), 4J (66), 39 (14) 129 (3
0), 27(13), 15(16) Reference Example 1 08 iB t s ■ 2-(]-]9ethylsilyloxy-2-chloro3.
ethyl 3-difluoro-2-global)-3゜3-dimethylcyclopropanecarboxylate 39 hexane l 25
) and 2-(1-hydroxy-2-chloro-3,
3-difluoro-2-propenyl)-3,3-dimethylcyclopropanecarbon [11! Ethyl 27~ was obtained.

Yield: 99 cm.

'H-NMR (CDCI, ): δ1,2-1.4 (m
, 9H), 1.5-1.8(m, IH), 1
．． 8-2.0 (m, 1i(), 2.3(bro
ad IH), 4. Ll-4,3(m, 2H)F
-NMR((,:1)(,113-CFCI,):δ
-87 (IF).

−91(IF) + Mass Cm/z (%)): 223(M −0Et
, 5), 142 (24), 141 (100), 127 (
32), 125 (12), 114 (19), 113 (9
2), 96 (14), 95 (53), 69 (19), 6
7 (38).

61 (14), 59 (37), 55 (14), 53 (1
3), 43 (33), 41 (39), 39 (22).

29(59), 27(25) Outgh Mass: C2H1oCIF202(M
Calculated value for '-0Bt): 223.0336.
Actual value: 223.0349 Reference example 2 Ethyl 2-(1-triethylsilyloxy-2,3゜3-trifluoro-2-propenyl)-3,3-dimethylcyclopropanecarboxylate 37In9 (0.1 mmo
Add 0.2M hydrochloric acid THF solution IR1 to
Stirred for 0 minutes. The reaction solution was filtered through a 7-glucose column, concentrated under reduced pressure, and purified with thin-layer chromatography (silica gel, acetic acid ether, 1:5).
-(1-hydro7-2゜3.3-trifluoro-2-
2,311 kg of ethyl propenyl)-3°3-dimethylcyclopropanecarboxylate was obtained. Yield: 91 cm.

'i(-NM几(CDCIs):δ 1.1-1.4(
m, 9H).

1.5-2.0 (m, IH), 3.1-3.4
(broad.

IH), 4.0-4.3(m, 3H)"k'-N
MR(C1)C13-CFCI3): a-102(
ddd.

J=6.33,8JHz, IF, -120(ddd.

J=1.37.47Hz, IF), -188(m, I
P) IR (neat): 3440, 2970,
l 791, 1730°1709.13L16,1
256,12]3,1175°1114.110LJ,
1072. ]L132,1018m114(12),1
13(78), l1l(27).

109(12), 96(11), 95(55), 69(
17), 67(36), 59(39), 55(19).

53(11), 43(31), 41(38), 39(2
1), 29 (60), 27 (23) + High Mass: C7) (10F302 (M −0
Calculated value for Et ): 207°0632. Actual value =
207.0673 Reference Example 3 1.1-difluoro-2-chloro-3-triethylsiloxane 1-) Lysocene 229 ~ THF5WLt solution K
1+t of IM hydrochloric acid methanol solution was added and stirred at room temperature for 40 minutes. After concentration under reduced pressure, purification with thin-layer chromatography (silica gel, dichloromethane-hexane 1:1) yielded 1.1-difluoro-2-chloro-1-tridecen-3-ol 1341 as a colorless oil. I got it. Yield 83%.

'H-NM几(CI)C13): δ 0.7-1.0
(m, 3H).

1.25 (s, 16H), 1-45-1.9 (m, 2H
).

1.77 (broad s, l H), 4.3
5-4.6 (m.

-91 (dd, IF) IR (neat): 338G (broad), 2945
．． 2875° 1747.128 + Mass (m/z (%)): 2sO (M −F20.
tr), 129(34), 127(100), 57(
22), 55 (14), 43 (39), 4] (25),
29 (15) + High Mass: C13H21CIF'2 (M -
) 120) Calculated value for K: 250.1299; Actual value: 25G, 1326 procedural amendment (voluntary) March 31, 1985 Director General of the Patent Office Michibe Uga 1, indication of the case 1985 patent application No. 87445 No. 2, Name of the invention Process for producing allyl fluoride derivatives 3, Person making the amendment Column 5 of "Detailed Description of the Invention" of the specification, Contents of the amendment l) Page 24, line 13 of the specification of the present application - . F2. cH=C(F)CF20SO2Me” is 1
n-C,. F2. CH=C(P)cF20802Me
J d Correct.

that's all

Claims (1)

[Claims] (1) The general formula RCH=C(X)CFX'Y is characterized by reacting an alcohol represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ with a halogenating agent or a sulfonylating agent. A method for producing an allyl fluoride derivative represented by the formula (in the formula, R
is an alkyl group, an aryl group, an alkenyl group, or a hydrogen atom; X is a halogen atom; X is a halogen atom, an alkoxyl group, an amino group, a thio group, an alkyl group, or a hydrogen atom; . )
.