JPH04139164A - Production of p-chlorophenylcarbamic acid ester - Google Patents

Abstract

PURPOSE:To simply obtain the title compound having weedcidal activity by using a carbamic acid ester obtained in a short process from readily available fluorobenzene or 2-fluoro-5-substituted oxyaniline, etc., as a starting substance and chlorinating the carbamic acid ester with a chlorinating agent. CONSTITUTION:A carbamic acid ester derivative [e.g. 1-methoxycarbonyl-2 methyl-2-propenyl(2'-fluoro-5'-cyclopentyloxyphenyl) carbamate] expressed by formula I [R is 1-4C alkyl (which may be replaced by halogen), alkenyl, alkynyl or cycloalkyl; R' is lower alkyl] is chlorinated using a chlorinating agent (especially preferably sulfuryl chloride) to provide the p-chlorophenylcarbamic acid ester expressed by formula II. The reaction is preferably carried out using benzene, toluene, acetone, etc., as a solvent and using a basic substance such as potassium carbonate as a catalyst at -20 to 150 deg.C for 10min to 10hr. This method can provide the objective compound simply in good yield.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a compound of the general formula The present invention relates to a method for producing a p-chlorophenylcarbamate ester represented by the following formula: alkynyl group; cycloalkyl group; Ro represents a lower alkyl group.

[Prior art and its problems] p-chlorocarbamate represented by the general formula (I+) is a compound having herbicidal activity as shown in JP-A-01-316,306, and its cyclization product The oxazolidinedione derivative is also a compound that has been disclosed to have extremely strong herbicidal activity.

However, the methods for producing these compounds are not satisfactory in terms of yield, and improvements have been desired.

As a result of intensive research to solve these problems, the present inventors found that the general formula (I) [Formula In the formula (1), R and Ro have the same meanings as above, and by chlorinating the carbamate ester represented by ko with an industrially easy oxygenating agent as a starting material, the formula (1) is obtained. The present invention was completed by discovering that p-chlorophenylcarbamate can be easily synthesized.

As is clear from the above description, an object of the present invention is to provide a method for producing the compound of general formula (I+) described above in good yield.

[Means for solving problems] That is, the present invention has the following configuration (1).

(1) - Formula (I) [wherein R represents an alkyl group having 1 to 4 carbon atoms, an alkyl group/alkenyl group which may be substituted with a halogen atom; an alkynyl group; a cycloalkyl group, and Ro represents a lower The general formula (I+) is characterized by chlorinating a carbamic acid ester recognized conductor represented by ] representing an alkyl group using a chlorinating agent [wherein R is an alkyl group having 1 to 4 carbon atoms, a halogen A method for producing a p-chlorophenylcarbamate ester represented by the following, which represents an alkyl group that may be substituted with an atom; an alkenyl group: an alkynyl group; and a cycloalkyl group.

(2) The above (1) using sulfuryl chloride as a chlorinating agent
).

(3) The above method using one or more inert solvents selected from benzene, toluene, xylene, tetrachloroethylene, hexane, hebutane, acetonitrile, acetone, N,N-dimethylformamide, dioxane, tetrahydrofuran, and dimethyl sulfoxide as a solvent. 1st (1st
).

(4) The above-mentioned using a basic compound selected from potassium carbonate, sodium carbonate, sodium hydride, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, triethylamine, trimethylamine, pyridine or dimethylaniline as a catalyst. No. (1)
Manufacturing method described in Section.

(5) The method according to item (1), wherein the reaction is carried out at -20 to 150°C for 10 minutes to 10 hours.

Next, a method for producing p-chlorocarbamate ester according to the present invention will be described.

In this reaction, a p-chlorophenylcarbamate of the general formula (TI) is obtained by reacting a carbamate of the general formula (I) with a chlorinating agent, preferably in an inert solvent, without a catalyst or in the presence of a base. It is something.

The inert solvent that can be used in this reaction may be one that does not inhibit the reaction, such as aromatic hydrocarbons such as benzene, toluene, and xylene, methylene chloride, chloroform,
Halogenated solvents such as tetrachloroethylene, hexane,
Examples include aliphatic hydrocarbons such as hebutane, aprotic polar solvents such as acetonitrile, acetone, N,N-dimethylformamide, dioxane, tetrahydrofuran, and dimethyl sulfoxide.

Although this reaction proceeds under non-catalytic conditions, a catalytic amount of a base may be used to speed up the reaction.

The reaction time is not limited, but is usually 10 minutes to 10 hours, preferably 30 minutes to 5 hours.

Bases that can be used in this reaction include inorganic bases such as potassium carbonate, sodium carbonate, magnesium oxide, sodium hydroxide, potassium hydroxide, sodium hydride, and sodium methoxide, or alkali metal alkoxides, triethylamine, trimethylamine, pyridine, and dimethylaniline. Organic bases such as

The reaction temperature of this reaction is not limited, but is between -20°C and
150°C, e.g. the boiling point of the solvent used, preferably lO~10
The product can be selected from the range of 0°C, and this reaction can be carried out by ordinary post-treatments such as removing the catalyst by washing with water or removing the solvent by distillation. Purification methods can also be used.

Examples and Reference Examples (manufacturing examples of bending conductors using carbamic acid according to the present invention) will be shown below to provide a more detailed explanation, but the present invention is not limited to these examples.

Example] 1-methoxycarbonyl-2-methyl- in a screw cap test tube
2-propenyl (2°-fluoro-5°-cyclopentyloxyphenyl) carbamate (107B.

0.3 mmol), dicyclohexylamine (7a+g
), tetrachloroethylene (2I11) and sulfuryl chloride (loOsg) were added, heated to 80°C and
Stir for hours.

After the reaction was completed, the mixture was washed with water and concentrated under reduced pressure to obtain a pale yellow viscous substance (102 mg).

This substance was confirmed to be 1-methoxycarbonyl-2-methyl-2-propenyl (2-fluoro-4'-chloro-5'-cyclopentyloxyphenyl) carbamate as a result of analysis such as 1-NMR spectrum. .

Yield 69%.

') I-NMRδ (CDCI,, PPM); 1.4
0-2.15 (1xH, br).

3.81 (3) 1. sl.

4.79 (IH, br).

5.16 (LH,br) 5.22 (lH, br).

5.50 (IH, brs).

7.06 (IH, br).

7.09 (IH, d, J+cr-9, 4Hz).

7.79(l)l,d,J++r-7,5)IZ)IR
v (wQ-1740, 1820cra-'Example 2 1-methoxycarbonyl-2-methyl-2-propenyl (2-fluoro-5°-n-hexyloxyphenyl) carbamate (120 mg) in a screw cap test tube.

o, +26 mmol), dicyclohexylamine (7 m
g) Add tetrachloroethylene (1wf) and sulfuryl chloride (loOmg), heat to 80°C and
Stir for hours.

After the reaction was completed, the mixture was washed with water and concentrated under reduced pressure to obtain a pale yellow viscous substance (127 mgl).

This is the result of analysis such as Jl-NMR spectrum 1-
Methoxycarbonyl-2-methyl-2-propenyl (2
It was confirmed that it was '-fluoro-4°-chloro-5-n-hexyloxyphenyl syncarbamate.

Yield 97%.

'H-NMRδ (CDCIs, PPM): 0.90
(3)1. br) 1.35 (81(, br).

1.85f3H, br).

3.80 (3H, S).

4, QQ(2)1. brt, J-6,8Hz).

5.16 (1) 1. br).

5.25 (If(,br).

5.50 (IH, brs).

7.11 (LH, brl.

7.12 (IH, d, JHr-10,4Hz).

7.79 (IH, d, JH, -7,9) 11) IR;
c,, J740,1620 cs-'Example 3 1-Methoxycarbonyl-2-methyl- in a screw cap test tube
2-propenyl (2°-fluoro-5°-propargyloxyphenyl) carbamate (177+eg.

0.55111o11, dicyclohexylamine (7
B), tetrachloroethylene (5IIi), and sulfuryl chloride (150 mg) were added, heated to 80°C, and stirred for 2 hours.

After the reaction was completed, the mixture was washed with water and concentrated under reduced pressure to obtain a pale yellow viscous substance.

This product was further recrystallized from ethanol to form a white solid (
151 mg) was obtained.

This is the result of analysis such as 'H-NMR spectrum.
-methoxycarbonyl-2-methyl-2-propenyl (
It was confirmed that it was 2°-fluoro-4-chloro-5-propargyloxyphenyl) carbamate.

Yield 77%.

’) l-NMRδ (CD (:1., PPM).

1.87 (3H, brs).

2.59 (LH, t, J-2,4Hz) 3.110 (3
8, S) 4.76 (2) 1. d, J-2,4Hz).

5.15 (LH,br) s, za (1o, br).

5.50 (IH, brs) 7.17 (18, d, Jor-10, 4H2).

7.26 (1) 1. br).

7.95 (ILd, J++p-7, HIZ)IR;
V co=1740.1620 C11-'cwc-2120 cm-' Reference example 1 1-methoxycarbonyl- in a 50 mλ eggplant flask
2-Methyl-2-propenyl (2°-fluoro-4-
Chloro-5'-cyclopentyloxyphenyl)carbamate (193a+g, 0.5 mmol), potassium carbonate (34+ag) and acetonitrile (IQmf) were added, and the mixture was stirred at room temperature for 5 hours.

After the reaction was completed, IN hydrochloric acid (2 mλ) was added, and ethyl acetate was added.
(2IlfLx3). The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a yellow oil.

This was recrystallized from ethanol as a white solid (170mg
) obtained.

This is the result of analysis such as 'H-NMR spectrum 3-
(2°-fluoro-4°-chloro-5°-cyclopentyloxyphenyl)-5-isopropylidene-1,3-
It was confirmed that it was oxazolidine-2,4-dione. Yield 96%.

'H-NMRδ (CDC1,, PPM) 1.45-2
．． 10 (8H, br).

2.06 (3N, s).

2.2!1 (3Ls).

4.72 (IH, br).

6.84 (18, d, JHy-fi, 1Hx).

7.29 (IH9d, JHr-9, IHz) IR, ν.

,. -1820, 1745 cm-g, p; 98.
3-100.1°C Reference Example 2 2-Fluoro-5-methoxy 7! Nilisocyanate (204 mg, 1.
Add 2 mg of methyl 2-hydroxy-3-methyl-3-butenoate (178 mg), and add toluene (30 mg).
ft) was added and dissolved.

While stirring this solution at room temperature, triethylamine (1
6 mg) was added dropwise, and after further stirring at room temperature for 30 minutes, IN
Hydrochloric acid (5mA) was added. This is ether (IQmf
After extraction with x3), drying with anhydrous magnesium sulfate,
Concentrate under reduced pressure.

The obtained yellow oil was purified using silica gel column chromatography to obtain a colorless oil (284B).

This is the result of analysis such as 'H-NMR spectrum 1
-methoxycarbonyl-2-methyl-2-propenyl (
It was confirmed that it was 2-fluoro-5°-methoxyphenyl) carbamate. Yield 80%.

'H-NMRδ (CDC1,, PPM).

IR 1,84 (3H, br, S).

3.77 (3H, s).

3.80 (3H, s).

5.15 (1) 1. br).

5.24 (IH, br).

5.50 (IH, brs), 6.52 (IH, ddd, J, r-4,5Hz, J-3
,6Hz,98.97(IN,dd,JHr-10,5
)1z, J-9,0Hz).

7.04 (1Lbr).

7.70(1)1. dd, JHr-7, 2Hz, J-3
, 6Hz); lyc-a-1740, 1625c
m-'0Hz).

Reference Example 3 2-fluoro-5-isopropoxyphenylisocyanate (298 mg) was placed in a 50 mj2 eggplant-shaped flask.

+, 5 mmol) and 2-hydroxy-3-methyl-
Add methyl 3-butenoate (219 mg) and add toluene (
30IIIL) was added and dissolved.

While stirring this solution at room temperature, triethylamine (2
1 mg) was added dropwise, and after further stirring at room temperature for 30 minutes, IN
Hydrochloric acid (5mj2) was added.

This was extracted with ether (10 mjl x 3), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.

The obtained yellow oil was purified using silica gel column chromatography to obtain a colorless oil (1 g of 389II).

This is the result of analysis such as 'H-NMR spectrum 1
-methoxycarbonyl-2-methyl-2-propenyl (
It was confirmed that it was 2'-fluoro-5'-isopropoxyphenyl) carbamate. Yield 80%.

') l-NMRδ (CDC13, PPhl); 1
．． 30(61(,d,J-6,2)1z).

1.84 (3H, brs).

3.80 (3H, s).

4.47 (II (, sep, J-8, 2Hz).

5.15 (IH, br).

5.24 (LH,br) 5.50 (IH, brs).

6.51 (1)1. ddd, JHF-4, 5) IZ,
J-3Hz GHz) 6.95 (IH, dd, J, r-10, 5) 1z, J
-9, QHx).

7.02 (ILbr) 7.69 (1M, dd, J, -6,8Hz, J-3,
6Hz) IR; C, 0-1740.1620
Cl11-' Reference Example 4 2-fluoro-5-cyclopentyloxyphenylisocyanate (877 m
g, 4.0 layer temperature o1) and methyl 2-hydroxy-3-methyl-3-butenoate (a50 mg) were added, and toluene (50 mJ2) was added to dissolve them.

While stirring this solution at room temperature, triethylamine (5
3I1g) was added dropwise, and after further stirring at room temperature for 30 minutes,
N-hydrochloric acid (1011 IL) was added.

This was extracted with ether (30ml x 3), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained yellow oil was purified using silica gel column chromatography to obtain a colorless oil (1.14 g).

This is the result of analysis of l-NMR spectrum etc. 1
~methoxycarbonyl-2-methyl-2-propenyl (
It was confirmed that it was 2°-fluoro-5°-cyclopentyloxyphenyl) carbamate. Yield 81%.

') I-NMRδ (CDC13, PPM) 1.5+
1-2.10 (IIH, br).

3.80 (3N, s).

4, δ9(1)1. br).

5.15 (IH, br).

5.24(1)1. br).

5.50 (18,brs).

6.48 (IH, ddd, JHy-4,5Hz, J”2
．． 9Hz, 9.1)lx).

8.95 (IH, dd, Jor"10.6Hz, J"
9.1Hz).

7, oa (u+, br).

7.88 (IH, dd, J++r-6,8) 1z, J-
2,9Hz) rR; vc-o-17404&2(
l cm-' Reference Example 5 2-fluoro-5-n-hexyloxyphenyl isocyanate (330
mg, 1.4a+mol) and 2-hydroxy-3-
Add methyl methyl-3-butenoate (taoIlg),
Toluene (10 mA) was added to dissolve.

While stirring this solution at room temperature, triethylamine (8
Hz1g) was added dropwise, and after further stirring at room temperature for 30 minutes,
N hydrochloric acid (2 mjN) was added.

This was extracted with ether (5ml x 3), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.

The obtained yellow oil was purified using silica gel column chromatography to obtain a colorless oil (1 g of 140II).

This product was confirmed to be l-methoxycarbonyl-2-methyl-2-propenyl (2°-fluoro-5°-n-hexoxyphenyl) carbamate as a result of analysis such as -NMR spectrum. Rate 27%.

') l-NMRδ (CDC13, PPM);0.
90(3)1. br).

1.32 (8H, br).

1.84 (3H, brs).

3.79 (3H, s).

3.H(2)1. brt, J-8, 21) 1z).

5.15 (Hl, br) 5.24 (IH, br) 5.49 (lH, brs).

IR・8.50 (IH, ddd, Jnr-4,5) 12. J-
2,9) IZ, 9.1H2).

6.95(II(, dd, JHr-10,4Hz, J-
9.1Hz).

7.09 (1) 1. br).

7.69 (1N, dd, JHr-6, 7H2, J-2
, 9) IZ) し, :, 0-1740.1620 C1
1-' Reference Example 6 2-fluoro-5-propargyloxyphenylisocyanate (150 mg,
0.8+mmol) and methyl 2-hydroxy-3-methyl-3-butenoate (102+sg) were added and dissolved in toluene (5ml).

While stirring this solution at room temperature, triethylamine (8
+ag) was added dropwise, and after further stirring at room temperature for 30 minutes, IN
Hydrochloric acid (1 m°C) was added.

This was extracted with ether (Smρx3), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained yellow oil was purified using silica gel column chromatography to obtain a colorless oil (177a+g).

This is the result of analysis such as 'H-NMR spectrum.
-methoxycarbonyl-2-methyl-2-propenyl (
It was confirmed that it was 2°-fluoro-5-propargyloxyphenyl) carbamate. Yield δ9%.

'H-NMRδ (CDCl2.PPM); 1.84
(3)1. brs).

2.52 (IH, t, J-2, 38Z).

3.79 (3H, s).

5.65 (2H, d, J-2, 3H2).

5.15 (IH, br).

5.24 (lH,br) 5.50 (IH, brs).

6.60 (IH, ddd, J, +r-4.5Hz, J-
3,1) 1z, 9.3Hz).

7.99 (IH, dd, JHy-10,6Hz, J-9
, 3Hz).

7.19 (IH, br).

7.78 (IH, dd, JH, -6,7Hz, J.3.
1) 1z) IR; v,,. -1740,162
0cva-'c, C-2120cm-'m, p,; 168, 1-170, 5
Reference Example 7 2-Fluoro-5-methoxyaniline (282 mg, 2.0 mmol) was placed in a 50aIL eggplant flask and dissolved in ethyl acetate (zmx). While stirring the solution at room temperature, add trichloromethyl chloroformate (0,
2 layers ft) were added dropwise.

The reaction solution was further raised to reflux temperature and stirred for 30 minutes, and then the solvent was distilled off. Carbon tetrachloride was added to the resulting residue and allowed to cool.

After removing the precipitated solid, the resulting solution was concentrated under reduced pressure to obtain a pale yellow oil (323 mg).

This is the result of analysis such as 'H-NMR spectrum 2
-Fluoro-5-methoxyphenylisocyanate was confirmed. Yield 97%.

') I-NMRδ (CDCIs, PPM); 3.
76 (3B, s).

6.53-6.75 (2FI, ■).

7.03 (l)1. ddd, JH, -9,9) II,
J-1,8Hz, 7.2Hz) IR; 11.
4cO-2270CI-Ren Reference Example 8 2-Fluoro-5-isopropoxyaniline (588 mg, 3.5 s serving) was placed in a 50 mA eggplant-shaped flask and dissolved in ethyl acetate (10 it). While stirring the solution at room temperature, trichloromethyl chloroformate (0,4IIJZ) was added dropwise.

The reaction solution was further raised to reflux temperature and stirred for 30 minutes, and then the solvent was distilled off. Carbon tetrachloride was added to the resulting residue and allowed to cool.

After removing the precipitated solid, the resulting solution was concentrated under reduced pressure to obtain a pale yellow oil (saswg).

This is ') I-NMR spectrum, etc. analysis result 2
-Fluoro-5-isopropoxyphenylisocyanate was confirmed. quantitative.

'H-NMRδ (II:DC13,PPM);1
．． 30 (6H, d, J-5, 9Hz).

4.42(l)1. sep, J-5,4Nlz).

6.51-6.73 (2) 1. ■).

7.01 (IH, ddd, IH4-9, 9Hz, J-
8,1Hz, 2.7Hz) IR, 5ea-2270
cm-' Reference Example 9 2-fluoro-5-cyclopentyloxyaniline (851 mg, 4.411
(2ol) was added and dissolved in ethyl acetate (10aIL). While stirring the solution at room temperature, trichloromethyl chloroformate (0.6 mJ2) was added dropwise.

The reaction solution was further raised to reflux temperature and stirred for 30 minutes, and then the solvent was distilled off. Carbon tetrachloride was added to the resulting residue and allowed to cool. After removing the precipitated solid, the resulting solution was concentrated under reduced pressure to obtain a pale yellow oil (877 g).

This product was confirmed to be 2-fluoro-5-cyclopentyloxyphenyl isocyanate as a result of analysis such as '1-NMR spectrum. Yield 90%.

'H-NMRδ (CDCIs, PPM); 1.5
0-2.10 (8H, br).

4.68 (IH, br).

6.50-8.72 (2H, ■).

7.00 (1B, ddd, JHr-9,9) 1z, J”
1.8Hz, Il, 1Hz) IR; '! l NC
0-2270C11-' Reference Example 1O 2-fluoro-5-n-hexyloxyaniline (510 mg, 2.4
*mol) and dissolved in ethyl acetate (20+cj!). While stirring the solution at room temperature, trichloromethyl chloroformate (0.5 g) was added dropwise.

The reaction solution was further raised to reflux temperature and stirred for 30 minutes, and then the solvent was distilled off. Carbon tetrachloride was added to the resulting residue and allowed to cool.

After removing the precipitated solid, the resulting solution was concentrated under reduced pressure to obtain a pale yellow oil (565 mg).

This is the result of analysis such as 'H-NMR spectrum 2-
It was confirmed that it was fluoro-5-n-hexyloxyphenyl isocyanate. quantitative.

'I(-NMRδ(CD(:1s, PPM);0.
80-1.12 (3H, br).

1, OO~1.60 (IIH, br).

3.8B (2H, brt, J=6.4Hz).

6.51~=6.72 (2L ■).

6.98 (IH, ddd, J, r-9, 5Hx, J-1
, 88x, 8.1Hz) IR; v NC0-22
70cm-' Reference Example 11 2-Fluoro-5-propargyloxyaniline (351 mg, 2.1 + amo
1) and dissolved in ethyl acetate (10111). While stirring the solution at room temperature, trichloromethyl chloroformate (0.2 f) was added dropwise.

The reaction solution was further raised to reflux temperature and stirred for 30 minutes, and then the solvent was distilled off. Carbon tetrachloride was added to the resulting residue and allowed to cool.

After removing the precipitated solid, the resulting solution was concentrated under reduced pressure to obtain a pale yellow solid (389+++g).

This is the result of analysis such as 'H-NMR spectrum 2
-Fluoro-5-propargyloxyphenylisocyanate was confirmed. Yield 97%.

') I-NMRδ (CDf:Is, PPM);2.
53 (l)1. t, J-2, 4) 1z).

4.63 (2o, d, +-2, u+z).

6.64-6.84 (28, Iri.

6.93-7.1B (IH, quantity) IR, Si wee-2270 C■-1 m, p,; 38.1-39.5°C Reference Example 12 2-Fluoro-5- in a 50 mjl eggplant-shaped flask Methyl methoxyphenylcarbamate (592mg).

3.0ml oil, ethanol (2+111) and 2
Aqueous N sodium hydroxide solution (10 x 1) was added, and the mixture was stirred for 2 hours under reflux.

Water (20 mA) was added to the reaction mixture, and ether (20 mA) was added to the reaction mixture.
sjL x3). The organic layer was diluted with water (10tIlx
3), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a brown oil (294 mg).

This is the result of analysis such as 'H-NMR spectrum 2-
It was confirmed that it was fluoro-5-methoxyaniline. Yield 89%.

'H-NMRδ (CDCI!, PPM); 3.72
(Hl,s).

8.18 (IH, ddd, kr-2, 7Hz, J-9,
0Hz, 3.8Hz>.

6.34 (IH, dd, JHr-a, IHlj-3,6
11z).

8.118 (LH, dd, JHy-9, 9Hz, J・9
．． 0I(z)IR; 3460,3370.183
0,1520.1210 cm-'Reference Example 13 Methyl 2-fluoro-5-isopropoxyphenylcarbamate (801s+g
.

3.51 ol), ethanol (Lose!), and a 2N aqueous sodium hydroxide solution (]omz> were added, and the mixture was stirred under heating under reflux for 2 hours.

Water (2omi) was added to the reaction mixture, and ether (20μ
fL x3). Water the organic layer (10 pieces 1 x 3)
The mixture was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a brown oil (604 mgl).

This is the result of analysis such as 'H-NMR spectrum 2-
It was confirmed that it was fluoro-5-isopropoxyaniline. quantitative.

'l(-NMR6(f:Dcls, PPM);1.
28 (6H, d, J-5, 4Hz).

3.67 (2) 1. br).

4.39 (IH, sep, J=8.4Hz).

6.111 (IH, ddd, J, y-3, 6) 1z,
J-2,,7Hz,9.0)Iz).

[i! 2 (It(, dd, Jor-7, 2) 1z,
J-2,7Hz).

6.85 (IH, dd, J, Iy-10, 4) 1z,
J-9,0Hz)IR; 3470,3380,29
80.1B45, 1520.1205 am-' Reference Example 14 In a 100 mft eggplant-shaped flask, methyl 2-fluoro-5-cyclopentyloxyphenylcarbamate (3,
0g, 11.8-■ol), ethanol (50 layer 1)
and 2N aqueous sodium hydroxide solution (IOaJl) were added thereto, and the mixture was stirred for 2 hours under heating and centrifugation.

Water (2hJ2) was added to the reaction mixture, and ether (2D
mj2 x 3). The organic layer was diluted with water (10+1jl
x3), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a brown oil (2.3 g).

This product was confirmed to be 2-fluoro-5-cyclopentyloxyaniline as a result of analysis such as -NMR spectrum. Quantitative.

'H-NMRδ (CDCI, , PPM); 1.50
~2.00 (8H, br).

3.65(2)1. br).

4.63 (IH, m).

6.16 (IH, ddd, Jsr-4, 5) 1z, J
-8,9Hz, 3.6Hz) 6.211 (IH, dd,
J, 4r-8, 1H2, J-3, 8Hz).

6.84 (IH, dd, JMr-11, 1H1j-1
1,98Z)rR: 3470,3380.295(
1,1635,1515,1205cll-'Reference example 1
5 Add methyl 2-fluoro-5-propargyloxyphenylcarbamate (550 mft) to a 50 mft eggplant flask.
fig, 2.5 mmol), ethanol (20 mft
) and 2N aqueous sodium hydroxide solution (IOaJl)
and stirred for 2 hours under heating and reflux.

Water (20+Ift) was added to the reaction mixture, and ether (20+Ift) was added to the reaction mixture.
0 mjl x 3). The organic layer was diluted with water (10mf
After washing with X3), it was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a brown oil. This was isolated and purified using silica gel column chromatography to obtain a white solid (270sg).

This is the result of analysis such as 'H-NMR spectrum 2
- It was confirmed that it was fluoro-5-propargyloxyaniline. Yield 65%.

'H-NMRδ (CDCIs, PPM); 2.50
2 (IH, t, J-2,4Hz).

3.72 (2H, br).

4.59 (2H, d, J-2, 4Hz).

6.26 (IH, ddd, J, -3,6Hz, J-3
, 1Hz, 8.78x).

6.39 (IH, dd, JH, -7, 1Hz, J-3
, 1H2).

6.88 (IH, dd, J, r-10,88x, J-
8,7)1z)IR; 3470,3380.298
0,1635,1515.1205 cm-'m, p,
; 59.2-61.8°C Reference Example 16 Isobutyl 2-fluoro-5-methoxyphenylcarbamate (591 mg) was placed in a 501J2 eggplant-shaped flask.

2.5 mmol), methanol (io+Jl) and 2
Aqueous N sodium hydroxide solution (1hj2) was added, and the mixture was stirred under heating under reflux for 2 hours.

Water (20 mj!) was added to the reaction mixture, and ether (2 mj!) was added to the reaction mixture.
011J2 X:l). The organic layer was diluted with water (10-
mA X3), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 2-fluoro-5-methoxyaniline as a brown oil (307J1g).

The results of this analysis were consistent with those described above. Yield 8
7%.

that's all

Claims (5)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R is an alkyl group having 1 to 4 carbon atoms, an alkyl group that may be substituted with a halogen atom; an alkenyl group ; Alkynyl group; represents a cycloalkyl group, and R' represents a lower alkyl group. General formula (II) characterized by chlorinating a carbamate ester derivative represented by ] using a chlorinating agent ▲There are numerical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R is 1 carbon number -4 represents an alkyl group, an alkyl group optionally substituted with a halogen atom; an alkenyl group; an alkynyl group; a cycloalkyl group. ] A method for producing p-chlorophenylcarbamate ester shown in the following. (2) The method according to claim (1), in which sulfuryl chloride is used as the chlorinating agent. (3) A patent that uses one or more inert solvents selected from benzene, toluene, xylene, tetrachloroethylene, hexane, hebutane, acetonitrile, acetone, N,N-dimethylformamide, dioxane, tetrahydrofuran, and dimethyl sulfoxide as a solvent. The manufacturing method according to claim (1). (4) A patent claim that uses a basic substance selected from potassium carbonate, sodium carbonate, sodium hydride, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, triethylamine, trimethylamine, pyridine, or dimethylaniline as a catalyst. The manufacturing method described in scope item (1). (5) The method according to claim (1), wherein the reaction is carried out at -20 to 150°C for 10 minutes to 10 hours.