JPS6242993A - Bis(3-acyloxypropyl)dialkoxysilane - Google Patents

Abstract

NEW MATERIAL:The compound of formula [RCO2(CH2)3]2Si(OR<1>)2 (R is H, 1-20C alkyl or aryl; R<1> is 1-5C alkyl or alkoxyalkyl). EXAMPLE:The compound of formula [HCO2(CH2)3]2Si(OCH3)2. USE:Modified silicone oil or varnish, silane-coupling agent, etc. It has excellent physical properties such as oleophilicity, surface-modifying capability and adhesivity, etc. PREPARATION:For example, 1 equivalent of bis(3-acyloxypropyl)dichlorosilane [e.g. (3-acetoxypropyl)dichlorosilane] is made to react with preferably >=2 equivalent of an alcohol (containing alkoxy group in the molecule) or its metallic salt in a solvent (preferably benzene, etc.) at 0-100 deg.C for 0.1-300hr.

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a novel organosilicon compound. <Prior art> Organosilicon compound having a 3-acyloxypropyl group,
For example, 3-acyloquinopropylalkylrealkoxysilane, 3-anroxypropyltrialkoxysilane 7, etc. are known, and they can be used as part I of modified silicone oil as well as as a furanic knobling agent. It is also known to act as a moisture crosslinking agent for alkylenealkylacrylic l/-1 copolymers (US Pat. No. 4.291. I 36 fj Specification M).
. <Problems to be solved by the invention> However, the conventional 3-(+xypropyl alkoxine rough)-based variant V1: Nrini]-no oil and varnish cannot be used in cosmetics, waxes, and electrical insulation. When used as a base for oil, water repellent, coating i-1, mold release agent, antifoaming agent, and lubricating oil, there are problems with physical properties such as lipophilicity.
When conventional 3-anthroquineprobyl alkoxylans were used as furanic force/knobling agents and moisture crosslinking agents, there were drawbacks such as low adhesiveness, surface modification ability, and hardness after treatment. <Means and effects for solving the problems> The present inventors have intensively researched the following methods to overcome the drawbacks of the prior art:
When it is made into a lease, it makes the lipophilic substance V1 towards I-, and at the same time acts as a coupling agent and water crosslinking agent.
A novel 3-ant 3-kimbe 11 that can improve surface modification ability, adhesion V1 and hardness after treatment in two cases.
The inventors discovered biralfoxysilanos and arrived at the present invention. That is, the present invention is based on the following general formula % [wherein R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms or an aryl group, and R1 is an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms] This is the first his(3-acyloxypropyl)noalcoquine silane represented by the following formula. In the above general formula, R represents a hydrogen atom or an alkyl group or aryl group having 1 to 20 carbon atoms, and specifically, in addition to the hydrogen side -r, methyl group, ethyl group, n-propyl group,
1S (1-propyl group, n-ethyl group, 5ec-butyl group, 1so-butylg, l:crt-butyl group, n-hezotatenol group,) 90 hequinol group, 4-methylnocy(]
]/\A-/Number of chain and cyclic carbon atoms in the group 1 + %
-In addition to 20 aliphatic hydrocarbon groups and phenyl groups, 4-menano-1 phenyl? tu, 4-kL] hekynyl7 ale group, 2, 4-nomethyl fugol group, etc. 1 or more tom or 1 chain or cyclic aliphatic hydrocarbon monohydrogen group 4)
The first one is an aryl group having 1 to 20 carbon atoms substituted with a rearrangement. In the above general formula, R1 is an alkyl group having a carbon atom number of 1 to 5,
Specifically, methyl group, ethyl%, n--frJ building group,
iso -=f II building group, n--ethyl group, SCI
'-ethyl group, iso--)tiJl/ group, +er
Chain alkyl J having 1 to 5 carbon atoms such as t-i del group
, (, methoxyethyl group, and a chain alkyl group having a total number of carbon atoms of 1 to 5, such as a methoxyethyl group and a methoxyethyl group). An example is rTTc
O, (CT(2)3J2 Si (ocH,,)2,
r TTCO2(CH,!) 3 ]2 S i (
OBun) 2, rCILCO□(CI-L),,
−]2Si(OCH,t)i, rCH,CO, (C
T1. )3]2 Si (QC21T,)2, [CI
lIC07(CI,", 5i(OCII(CTT)
:+)z)2, [CTl1CO3(CTT2)j]2S
1 (OI] Y6) 2, [CIL CO, (CJL)
+′□],, S 1rOc(cH,+)a]z,rC
I■,C04(C[i+12Si(OBu')7,[C
T-T, CI C('), (CIL)332Si (O
CTIl)2,c CI(,<CiL) l l
, C02 (CT): 1. S i (0OT+)
2, cClLCH, Co, (CTL), hS
i (OBLIn)2, [CH, (CTL)+aCO
z'(CI'Ll),]2si (OCHII)2
, cPhC02(CJL):+]2Si (OCIL)
2. (PhCO, (CILh)2Si(OBu”)2, cH
co, (CTL):+h Si (OCH2C,H,,
0CT(,) , [CFLCo□(CT+]2S
i (OCH2(NT20CTr, ) 2.1CT
(jCO,, (CH,),, 112 S i (OC
H,,CTT2QC2T-T5) 2,('PliCC
), (CH2) 3 )2 S 1 (OCL o■2
ocri, )2, the compounds of the present invention can be produced by any method. The method for producing the compound of the present invention is as follows:
For example, Nishihis(3-acyloxypropyl)chlorone alcohol or alcoholy J & 4r has 1 in the molecule.
- Li method of reacting with alcohol, facial hissing (3-
acyloquine zolovir) Ninoki "1 [] A method of reacting cyrano with an alcohol or a metal salt of an alcohol having an alcoquine group in the molecule, 0 Allyl 1 sprue of carboxylic acid and dialcoquine,
Examples include a method in which a metal salt of carbonic acid is subjected to a hydrosilylation reaction, and a method in which a metal salt of carbonic acid is subjected to a substitution reaction with a his(:1-propyl)-alcokyne silane. The Ij method for F1 will be specifically explained below. In the method, for the purpose of neutralizing the by-produced hydrochloric acid,
/ can also be introduced into the reaction system. In that case, it may be difficult to stir the hydrochloride of the amine that is produced, so benzene, quince, 1-thyl, 'I''HF, hex→l, petroleum gothyl, It is preferable to use ligroin or the like as a reaction solvent.The reaction can be carried out by mixing and stirring raw wood and a reactant in a solvent. Alcohols or alcohols having an AlcoA group in their molecules or their metal salts can be reacted at any ratio (molar ratio), but preferably at a ratio of 1:2 (molar ratio) to ensure complete reaction. The reaction temperature is -30 to 150°C, preferably 0 to l
Q O'C. The reaction time depends on the amount of reaction solvent, reaction temperature, lumber ratio, etc.
It is possible to change the time within the range of 0.1 to 300 hr. The reaction can be carried out either under normal conditions or under pressure. The compound of the present invention can be isolated from the reaction mixture thus obtained by a conventional method. For example, the target compound can be isolated and purified by distillation under reduced pressure or column chromatography.・, Examples〉 The compounds of the present invention will be specifically explained in the following Examples, but the Examples of Son will be explained based on some examples of the present invention. ), does not limit the scope of the claims. Example 1 His(3-acetoquinopropyl)ink [II] Norashi 59.3F, 66 g of l-ethylamine was placed in a reactor made of f: 1 # forceps equipped with a stirrer, a dropping funnel, and a temperature a1.
/, Baise, -600 shoulder t was charged, and while stirring and keeping the reaction temperature below 10°, 7-'l of Metatsuru 15.29 was added dropwise in 90 minutes. After that, the temperature of the reaction solution was returned to room temperature, and stirring was continued for another 1 hour. After the reaction, triethylamine hydrochloride was filtered. After that, the reaction solution was distilled to obtain a product 48 with a boiling point of 141-142℃ 7'151Hg. .91 was obtained (yield 85%). Infrared absorption spectrum of the obtained product 11.
I-,-,-1-1 of nuclear magnetism.
and FIG. 2, respectively. The infrared absorption vector is the absorption of carbonyl of acetate ester at 1740m, and the absorption of carbonyl of acetate ester at 1740m, and the
showed strong absorption. In addition, the nuclear magnetic resonance spectrum measured in the CDCI had a (δ value) of 4.07 P (t
,4fICTTlCO2CIT,'J ,3.60 (
s, 6HS+-0CI(+), 2. I O(s
, 6HCH4C(%C)L-), 1.5-2.
I (m, 4HCTTlCo, CTT, CT(,,
CH25i), 0.5-1.0 (m, 4HCTL
CO, , CJI2CH2CILSi) with a signal of 1<
Cj2. The mass spectrum is determined using the CI method (chemical ionization method).
zationmethod) using inbutane, M −+1, = 293 Peters were measured.

【Ta. The structure of the compound obtained from the following I-take is (CTTI
I C(-)2 (CH2) :+ )2 S l (
0C1I: + 'I Confirm that it is 2 and press I. Example 2 A lot of his(:ooacetoxyp[copyl)dichlorosilane] and 48 g of isopropyl alcohol were reacted under the same reaction conditions as in Example 1, resulting in a boiling point of 153-154°C/3.
mHg product 9.4f was obtained (yield as high as 81). ? The line absorption subek I of the product of iJ is 17
Apply acetic acid nisful to 40 cm.
-C shows absorption. In addition, 1025n (5l near J)
It shows strong absorption of -0-C. In addition, the nuclear magnetic t (sound spectrum) measured in CDCl was (δ value) 3.9 to 4.4 (m, 6TICI
T,CO□CJLCILCILSi(ICJf(CH,
,)2),2. 0 6 (s. 6 H (-11=COzCH2-), 1.3-2.
] (rn, 4 ITClllCO, CfICI
(, CT(28i), 1.18 (d, +21
(S]CF((CIT+)2), 0.3~0
．． 8 (ITS, 411CIT, C02C+I,
CJj, CT (2S i), small amount of Gunar. Mass spectra were obtained using the CI method (chemical
zationmethod) using ammonia.
In two cases, a peak of M −+18-366 was measured! =
. One compound of J'l obtained from my son's take is (CIT,
C02(CIL), :125i(OCH(CI(i,
] At 2, - confirm. Example 3 His(3-acetoxyb-l]pyr)dichlorosilanoIOy and 7dylcelnorb5 were reacted under the same reaction conditions as in Example 1.
58g was reacted, boiling point 1 fi 5~170°C,
/ 10.742 f of one product of 1.2 T1 g was obtained. The obtained tKono4 parabolic Red Sun 1-ray absorption Subek] is 1
The carbonyl absorption of acetate ester is shown at 74 oz. Furthermore, strong absorption of S]-0-C is shown at +090/m'. - The CDC1, in which 1llll + determined nuclear magnetism JI
, the sound spectrum is (δ value) 4.03 (11,4TI)
, 3.88 (L, 4H) , 3.45 (1,lI
), 3.40 (s, 6II), 2.05 (s,
6H), 1.45-2. Signals are shown at OO (m. 411), 045-090 (m, 4■■). Mass spectrum is Ml-+18 by CI method (ammonia)
= 398 peaks were measured. The compound obtained from the above data is cCH,Co□(Cl+]2S](0C
Confirm that T-T2 CH20CtT.Example 4 Stirrer, drop Fr1. -1, Wensheng Ha 1? 11)? ,−
200d (D Hiss (:3-A I) in the Kermis reactor
! Tokinopu I-1 Building) Nokeroro 7.9715g, 1-
Richo-f no 1 a ζ, 12y1 Henose-100z (I 1
Add 10'('KJ 100% reaction at, t, without stirring, terl-futamer 88]) over 10 minutes. Return,
The mixture was further stirred for 1 hour and then carbonized for 6 hours. After reaction, l-I
After filtering the I-r-f amine hydrochloride for 7 hours, the reaction solvent was distilled off, and the reaction mixture was added to a 50 ml [11] If-7 reactor, and 5 ml of THF was added. Nipotassium tert-
Butoand (90% pure, 1,53 y) was heated to room temperature [
After dropping TITF with ζ for 10 hours, force → l・ri "171-graph(r(ieselgel)
60 art, 7733, developing solvent: acid-resistant ethylchlorhexane=■/3) to isolate product 1.591. The infrared absorption spectrum of the first product obtained is +74:1
Add the carbonyl absorption of acetate ester to m. Furthermore, 050 rys-' shows strong absorption of 5i-(1-C. Also, the t: nuclear magnetic resonance spectrum measured in CDCl is (δ value) 4.03 (t, 4H), 2 .06 (
s. 6H), 1.3-2.0 (m, 4H), 1.31'
(S. 18H), signals are shown at 0.4-0.9 (m, 4H). The mass spectrum is M when ammonia is used by the CI method.
+ l 8 = 394 peaks were measured. The compound obtained from the above data is [CH3Co2(CH,)2Si rOc(cH, +
)J], confirm that it is +. Example 5 Under the same reaction conditions as in Example 1, 5.873 y of his(3-butyloquinopropyl)dichlorosilane and 1.
] 58 y to a boiling point of 150-154℃/
0.49 mHg product 4.097 f'i-obtained
child. The infrared absorption spectrum of the obtained cow parallax is 1737
Absorption of carbonyl of butyrate ester in m-', and further I
Strong absorption of 5i-0-C was observed near O80nx'. Also measured in CI) C13, the sound spectrum was (δ value) 4. (12(t, 4T() , 3.54
(s. 6IT), 2.27 (L, 4T(), 1.3~2
．． 0 (m. 8H), 0.5-1. ．． 1 (m, 10H) shows a signal. The mass spectrum was obtained using the Cr method <Fummonia> M118
= 36 (the peak of 1 was measured). The structure of the compound obtained from the following data is CCITI
C)L CFL C(% (CH2) 1:' 2 S
l (0CTT:l) Confirm that it is 2. Example 6 Into a reaction vessel for the argon purging method, equipped with a cyclolon run inlet pipe, an acetono-dry ice cooler, a rotor, and a temperature gauge 1, an ionobanol solution of allyl benzoate 10.932 and chloroplatinic acid (a %) 1112111
0.0337 mol of dichlorosilano was introduced in 27 minutes through the dichlorosilano/introduction tube, while maintaining the reaction temperature at 77°C to 88°C, while heating and stirring. The reaction mixture was heated for 7 hours and reacted with 259 g of methanol under the same reaction conditions as in Example 1.
rt, 7733, Lit separation and purification was performed using a developing solvent of 3.19
! The product of is t() from A]. Rf value of thin layer of product IJ7 Togelafy (Merck Kiesel Gel 6
0 F 254, developing solvent Nzu)/ll! 1
Ethyl acid (4/'l) was 0.57. hmm! 171j The infrared absorption spectrum of the adult cow is 17
At 20(7)-1, carbonyl absorption of folic acid ester occurs, and furthermore, 5i-0-C(+
) Has strong absorption. CI) CI, the nuclear magnetic field I (Narusu/Fire Tor) measured in CI (δ value) 8.06 (m, 4H), 7.46
(nl. 6H), 4.30 (t, 4H), 3.58 (s
, 6H), 15-2.2 (m, 4H), 0.5-1
．． 0 (m, 4T-T). Elemental analysis measured values C: 63.34, H: 6.92 (
Word arithmetic (1 white C: 6 3. 4 4,
Tl: 6. 7 8) Tea -
) tko. The structure of the compound obtained in 11 is (C
,T(,C02(CIL) 3-128 i(OCT
Yes, I confirmed that there was -C. Effects of the Invention The compounds of the present invention are novel compounds and are useful as intermediates for the synthesis of novel organosilicon compounds. Using the compound of the present invention as a raw material: SR Reno J'l It is useful as a base material for antifoaming agents, etc. It is also useful as a silano coupling agent and a water crosslinking agent.

[Brief explanation of drawings]

Figures 1 and 2 show the Red Sun 1-ray absorption spectra of the compound of the present invention, His(3-A7Hkinpropy+l), nuclear magnetic resonance spectra. -1 is shown in the first column. Patent Applicant Toshi Co., Ltd. Written Amendment to Procedures ()) 1. Case description 1985 Patent Request No. 182545 2 Name of invention Bis(3-acyloxypropyl)sial]xysilane 3
, Relationship with the case of the person making the amendment Patent applicant address: 103 I1 Chuo-ku, Tokyo]] Honyokomuromachi 2-2-4,
Date of amendment order: November 260, 1985 (Shipping [1)] 7. Contents of amendment Figures 1 and 2 of the drawings will be amended as shown in the attached sheet.

Claims (1)

[Claims] The following general formula [RCO_2(CH_2)_3]_2Si(
OR^1)_2 [In the formula, R is a hydrogen atom or 1 carbon atom
-20 alkyl or aryl groups, R^1 represents an alkyl or alkoxyalkyl group having 1 to 5 carbon atoms] bis(3-acyloxypropyl)dialkoxysilane.