POLYFLUOROALKYL ALLYL COMPOUND AND METHOD FOR PRODUCING THE SAME

Abstract

A polyfluoroalkyl allyl compound represented by the general formula:

CF.sub.3(CF.sub.2).sub.n(CH.sub.2CF.sub.2).sub.a(CF.sub.2CF.sub.2).sub.bCH.sub.2CH═CH.sub.2  [I]

(n: 0 to 5, a: 1 or 2, b: 0 to 3). The polyfluoroalkyl allyl compound is produced by reacting a carboxylic acid allyl adduct represented by the general formula:

CF.sub.3(CF.sub.2).sub.n(CH.sub.2CF.sub.2).sub.a(CF.sub.2CF.sub.2).sub.bCH.sub.2CHICH.sub.2OCOR′  [II]

(n, a, and b are as defined above, and R′: a C.sub.1-C.sub.3 alkyl group) with a transition metal. This method for producing provides a polyfluoroalkyl allyl compound used as a synthetic intermediate for a fluorine-containing alkylsilane compound that can remove free iodine derived from the raw material compound, before a hydrosilylation reaction is performed, without using a metal reagent having a high environmental impact, and that has excellent handling properties.

Claims

1. A polyfluoroalkyl allyl compound represented by the general formula:
CF.sub.3(CF.sub.2).sub.n(CH.sub.2CF.sub.2).sub.a(CF.sub.2CF.sub.2).sub.bCH.sub.2CH═CH.sub.2  [I] wherein n is an integer of 0 to 5, a is 1 or 2, b is an integer of 0 to 3.

2. A method for producing the polyfluoroalkyl allyl compound according to claim 1, the method comprising reacting a carboxylic acid allyl adduct represented by the general formula:
CF.sub.3(CF.sub.2).sub.n(CH.sub.2CF.sub.2).sub.a(CF.sub.2CF.sub.2).sub.bCH.sub.2CH ICH.sub.2OCOR′  [II] wherein n is an integer of 0 to 5, a is 1 or 2, b is an integer of 0 to 3, and R′ is a C.sub.1-C.sub.3 alkyl group, with a transition metal.

3. A carboxylic acid allyl adduct represented by the general formula:
CF.sub.3(CF.sub.2).sub.n(CH.sub.2CF.sub.2).sub.a(CF.sub.2CF.sub.2).sub.bCH.sub.2CHICH.sub.2OCOR′  [II] wherein n is an integer of 0 to 5, a is 1 or 2, and b is an integer of 0 to 3, and R′ is a C.sub.1-C.sub.3 alkyl group.

4. A method for producing the carboxylic acid allyl adduct according to claim 3, the method comprising reacting polyfluoroalkyl iodide represented by the general formula:
CF.sub.3(CF.sub.2).sub.n(CH.sub.2CF.sub.2).sub.a(CF.sub.2CF.sub.2).sub.bI  [III] wherein n is an integer of 0 to 5, a is 1 or 2, and b is an integer of 0 to 3, with carboxylic acid allyl R′COOCH.sub.2CH═CH.sub.2 having a C.sub.1-C.sub.3 alkyl group (R′).

Description

EXAMPLES

[0032] The following describes the present invention with reference to Examples.

Example 1

[0033] A 1000-ml three-necked flask was equipped with a dropping funnel and a Dimroth condenser in the presence of inert nitrogen gas. 400 g (0.66 mol) of polyfluoroalkyl iodide CF.sub.3(CF.sub.2).sub.3(CH.sub.2CF.sub.2)(CF.sub.2CF.sub.2).sub.2I was charged in the three-necked flask, while 74.0 ml (0.69 mol) of allyl acetate CH.sub.2═CHCH.sub.2OCOCH.sub.3 and 2.61 g (6.5 mmol) of a radical initiator P-16 [di(tert-butylcyclohexyl) peroxydicarbonate] were placed in the dropping funnel, respectively, and the content of the three-necked flask was stirred. When the temperature reached 90° C., droppings from the dropping funnel was started to initiate reaction. Heat generation became weak in the latter half of the reaction; therefore, 0.09 g of P-16 was added to allow the reaction to continue.

[0034] Two hours later after completion of the heat generation, the temperature was cooled to room temperature. The reaction mixture was analyzed by NMR and gas chromatography to confirm the structure and conversion of the reaction product. The conversion of the target product was 87%. Unreacted raw material compounds were removed by vacuum distillation, thereby obtaining 391 g (95% GC, yield: 84%) of light yellow solid allyl acetate adduct.

CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CHICH.sub.2OCOCH.sub.3 [0035] .sup.19F-NMR (d-acetone, 282.65Hz):

−80.2:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−110.3:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−112.2:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−120.2:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−121.9:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−122.5:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−124.9:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

Example 2

[0036] A 500-ml three-necked flask was equipped with a dropping funnel and a Dimroth condenser in the presence of inert nitrogen gas. 180 ml of methanol and 20.1 g (0.33 mol) of Zn were placed in the flask, while 200 g (0.28 mol) of the allyl acetate adduct obtained in Example 1 and 20 ml of methanol were placed in the dropping funnel, respectively, and the content of the three-necked flask was stirred. When reflux started to occur, droppings from the dropping funnel was started to initiate reaction. After dropping, the resulting mixture was stirred for 2 hours, and then cooled to room temperature to stop the reaction.

[0037] Since the phase separation of the reaction mixture was unclear, an attempt was made to cause liquid separation by distilling off the methanol; however, an emulsion was formed. Accordingly, the precipitate was filtered, followed by liquid separation again and drying, thereby obtaining 123.7 g (92% GC, yield: 77%) of the target compound, i.e., a transparent liquid terminal allyl compound. In this reaction, it was confirmed that the reaction proceeded with good reproducibility, irrespective of the purity of the starting material. Next, vacuum distillation was performed to increase the purity to 97% GC.

CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH═CH.sub.2 [0038] .sup.1H-NMR (d-acetone, 300.4 Hz):

δ5.9−5.7:—CF.sub.2CH.sub.2CH═CH.sub.2(m)

5.4:—CF.sub.2CH.sub.2CH═CH.sub.2(m)

3.6:—CF.sub.2CH.sub.2CF.sub.2—(quin)

3.0:—CF.sub.2CH.sub.2CH═CH.sub.2(dt) [0039] .sup.19F-NMR (d-acetone, 282.65 Hz):

−80.2:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−110.2:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−111.9:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−120.3:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−121.9:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−122.1:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−122.5:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−124.9:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

Reference Example 1

[0040] A 100-ml three-necked flask was equipped with a septum and a Dimroth condenser in the presence of inert nitrogen gas. 20.0 g (0.04 mol) of the terminal allyl compound obtained in Example 2 and 5.8 ml (0.05 mol) of triethoxysilane were placed in the three-necked flask. The content of the three-necked flask was stirred, and the temperature was increased to 80° C. After the temperature increase, 20 mg (0.05 mol % based on the terminal allyl compound) of chloroplatinic acid H.sub.2PtCl.sub.16.Math.6H.sub.2O was added to initiate reaction. After stirring for the whole day and night, the reaction mixture was cooled to room temperature to stop the reaction.

[0041] The reaction mixture was subjected to vacuum distillation, thereby obtaining 10.7 g (yield: 42%) of the target compound, i.e., a transparent liquid terminal triethoxysilylpropyl derivative.

CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.2CH.sub.3).sub.3 [0042] .sup.1H-NMR (CDCl.sub.3, 300.4 Hz):

δ3.83:—Si(OCH.sub.2CH.sub.3).sub.3(q)

2.92:—CF.sub.2CH.sub.2CF.sub.2—(quin)

2.13:—CH.sub.2CH.sub.2CH.sub.2—(tt)

1.75:—CH.sub.2CH.sub.2CH.sub.2—(m)

1.21:—Si(OCH.sub.2CH.sub.3).sub.3(t)

0.70:—CH.sub.2CH.sub.2CH.sub.2—(t) [0043] .sup.19F-NMR (CDCl.sub.3, 282.65 Hz):

−82.2:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−113.2:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−115.6:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−122.5:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−124.0 to −126.0:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−127.:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

Reference Example 2

[0044] A 100-ml three-necked flask was equipped with a septum and a Dimroth condenser in the presence of inert nitrogen gas. 20.0 g (0.04 mol) of the terminal allyl compound obtained in Example 2 and 4.8 ml (0.05 mmol) of trichlorosilane SiHCl.sub.3 were placed in the three-necked flask. The content of the three-necked flask was stirred, and the temperature was increased to 40° C. After the temperature increase, 14.5 mg (0.1 mol % based on the terminal allyl compound) of Karstedt's catalyst (Pt.Math.CH.sub.2═CHSiMe.sub.2OMe.sub.2SiCH═CH.sub.2) was added to initiate the reaction. The oil bath temperature was gradually increased. When the temperature reached 100° C., the temperature was maintained at a constant, and stirring was performed for the whole day and night. After the disappearance of raw materials was confirmed by NMR, the reaction was stopped by cooling the reaction mixture to room temperature.

[0045] Next, without purifying a terminal trichlorosilyl product produced by this reaction, 3.7 ml (0.05 mol) of methyl orthoformate CH(OCH.sub.3).sub.3 was added thereto, and the mixture was heated to 40° C. After confirming that the reaction solution became homogeneous, 5.6 ml (0.15 mol) of methanol was added, and the mixture was stirred for 1 hour, followed by distilling off of low-boiling components and vacuum distillation, thereby obtaining 10.10 g (yield: 41%) of the target compound, i.e., a transparent liquid terminal trimethoxysilylpropyl derivative.

CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2CH.sub.2Si(OCH.sub.3).sub.3 [0046] .sup.1H-NMR (CDCl.sub.3, 300.4 Hz):

δ3.58:—Si(OCH.sub.3).sub.3(s)

2.92:—CF.sub.2CH.sub.2CF.sub.2—(quin)

2.12:—CH.sub.2CH.sub.2CH.sub.2—(tt)

1.74:—CH.sub.2CH.sub.2CH.sub.2—(m)

0.72:—CH.sub.2CH.sub.2CH.sub.2—(t) [0047] .sup.19F-NMR (CDCl.sub.3, 282.65 Hz):

−82.1:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−113.2:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−115.6:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−122.5:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−124.0 to −126.0:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−127.0:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

Comparative Example

[0048] In Reference Example 2, 30 g (0.08 mol) of C.sub.6F.sub.13CH.sub.2CH═CH.sub.2 was used in place of the terminal allyl compound, and the amount of the Karstedt's catalyst was changed to 31.6 g (0.1 mol % based on the terminal allyl compound), the amount of trichlorosilane was changed to 10.1 ml (0.105 mol), the amount of methanol was changed to 12 ml (0.30 mol), the amount of methyl orthoformate was changed to 7.7 ml (0.1 mol), and the temperature to react with trichlorosilane was changed to 60° C., respectively. As a result, 31.66 g (yield: 79%) of a transparent liquid terminal trimethoxysilylpropyl derivative was obtained.

CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3 [0049] .sup.1H-NMR (CDCl.sub.3, 300.4 Hz):

δ3.63:—Si(OCH.sub.3).sub.3(s)

2.10:—CH.sub.2CH.sub.2CH.sub.2—(quin)

1.81:—CH.sub.2CH.sub.2CH.sub.2—(m)

1.74:—CH.sub.2CH.sub.2CH.sub.2—(t) [0050] .sup.19F-NMR (CDCl.sub.3, 282.65 Hz):

−82.0:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−115.6:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−123.1:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−124.0:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−124.8:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

−127.3:CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2—

Reference Example 3

[0051] Substrate: Matsunami Glass (Preclean water edge polishing S7213)

[0052] Solution: 100 g of Vertrel, 0.1 g of sample, 40 mg of 0.05 M hydrochloric acid, and 5 ml of methanol

[0053] Coating conditions: spin coating, 0.5 g, 1000 rpm, 30 seconds

[0054] Drying conditions: 23° C., 50% RH

The following table shows the results of the measurement of the contact angle of each sample under the above conditions.

TABLE-US-00001 TABLE Contact angle (°) No. Sample H.sub.2O Hexadecane 1 Ref. Ex. 1 108 69 2 Ref. Ex. 2 108 69 3 C.sub.6F.sub.13CH.sub.2CH.sub.2Si(OEt).sub.3 106 63 4 Comp. Ex. 106 73 5 C.sub.8F.sub.17CH.sub.2CH.sub.2Si(OEt).sub.3 109 69