JPS59199696A - Compound having lipid-like structure and polymer and their preparation - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R is biphenyl, phenyl, -CmH2m+1 R' is H, -CmH2m+1; m, n are integers). EXAMPLE:[2-(methacroyloxy)ethyldimethylammonium]p-diphenyl phosphate. USE:Temperature sensor, gas sensor, ion-permeation membrane, artificial organs, cell fusion, enzyme immobilization, biosensor and cultivation. It can be made into strong membranes. PREPARATION:The reaction of a compound of formula III such as a compound of formula IV with a compound of formula V such as N,N-dimethylaminoethyl methacrylate is conducted in a solvent such as acetonitrile to give the compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to compounds and polymers having structures similar to phospholipids, and methods for producing the same.

(Prior Art) It has been revealed that living organisms contain many types of phospholipids, and these phospholipids play an important role in maintaining the life of living organisms.

For example, phospholipids are components of cytoplasm such as cell membranes, and are closely related to various metabolic processes in living organisms. It also plays a very important role in taste perception.

Since phospholipids have many functions in supporting overall life, many attempts have been made to apply them to various artificial organs, cell fusion, enzyme immobilization, artificial cultivation, biosensors, etc.

However, the phospholipids generally used in these attempts, such as lecithin, phos-7 atidylethanolamine, and phos-7 atisorserin, are all natural products extracted from living organisms.
Due to its low molecular weight, it is extremely difficult to obtain a uniform and strong film.

Therefore, in order to be used in the above-mentioned fields such as humidity sensors, gas sensors, ion-permeable membranes, artificial organs, cell fusion, enzyme immobilization, biosensors, and artificial cultivation, these must be obtained from relatively high polymers and must be strong. There is an extremely high demand for these materials to be able to be formed into films and to be highly economical.

(Objective of the Invention) In order to eliminate these problems and meet the above-mentioned demands, the object of the present invention is to provide a compound having a structure similar to that of a phospholipid and a method for efficiently producing the same.

(Structure of the Invention) That is, the present invention provides a phospholipid-like structure represented by the general formula % -H, -CrnH2m+x (where m and n represent integers). The gist is the compounds that have

The present invention will be explained in detail below.

(Structure and Examples of the Invention) First, for example, literature (Makromol, Chem,
, Rapid Commun, 3, 457-459 (1
982) or PolymerPreprints,
Japan, pages 2735-2738. vol
, 31.

According to the method described in N[Llo), the following formula (4)
(5) <2-oo-1,3,2-v oxyphosphorane (I) t-synthesized.

(1) Using the produced compound (1) and p-phenylphenol, the following formula (6) % 3.2-sooxaphosphorane (compound ■) was synthesized according to the method described in the same document.

(If) In place of the above p-phenylphenol, p is replaced by phenol, n
-dodecyl alcohol, n-hexyl alcohol, n-
A compound (DI) according to the following general formula was synthesized by reaction using ff-rualcohol, n-7'lopylalcohol, or ethylalcohol.

(I[l) (in the formula, R is -(J5-(=〉, b), -〇□H2□+1
8, or m represents an integer).

Next, 0.1 mol of the above-mentioned compound (It) and N, N-
Tsumethylaminoethyl methacrylate (CIF(2=C
(CT(3) CO2(CH2),,N(CH3)2)
0, 1% k't: 300 crA (D
7 Dissolve in tonitrile and put in a pressure bottle at 50-60℃
The mixture was allowed to react for 30 hours while being shaken. After the reaction was completed, the acetonitrile in the solution was distilled off under reduced pressure, and the residue was poured into a large excess of acetone, the solution was allowed to stand still, the supernatant liquid was discarded, and the residue was collected. After repeating the same operation three times, the residue was dried under vacuum, and the dried residue was further dissolved in methyl alcohol, filtered using absorbent cotton, the filtrate was added dropwise to a large excess of acetone with stirring, and after standing, The clear liquid was discarded. The same operation was repeated 2 to 3 times, and the resulting product was vacuum dried and then weighed, and the yield was about 75%. The elemental content and infrared absorption analysis results of this product are shown in Table 1 and Figure 1 below.
From these analysis results, the product is [2-(mu]p-sophenylphos7) produced by the reaction of formula (7) as follows.
ate (compound ■).

Table 1 0CH2cH2N(CH3)2 II3 CL 0- (IV) When the above-mentioned acetonitrile substitute is reacted with trimethylformamide (DMF) or methyl alcohol as a solvent, there is a slight difference in yield, but the above-mentioned The same compound (IV) as in the case was obtained.

Next, any one of the compounds (In) synthesized using the above various alcohols was reacted in the same manner as above using any one of the above N,N-dimethylamamimythyl methacrylates, and the resulting product was identified. It was confirmed that it was compound (V) of the following formula (8), which had a similar structure to compound (IV).

0CR2CH2N(CH3)2 CH3 CH2=C C=OCH30 111 OCR,CH2-N"-CH2CH2-0-P-OR-
...(8) 1 1 C 〇- (V) Next, substitute N, N-noethylamine ether methacrylate (
CH2= C(CH3) cot (CH2)2N(C
2H5) 2), N,N-so1ao-globylaminoethyl methacrysate (CH2=C(CHs)CO
t(CL)2Nl:CH(C)LJ2)) , N, N
-N-n-butylaminoethyl methacrylate) (CH
2= C(CH3)CO2(CH2)N ((CH2)
3CH3)2), N-methylaminoethyl methacrylate (CH2= C(CH,)C02(CH2)
2NH(CH3) ) , N -xf Ruami/Engakuflume Iri') v -) (CH2=C(CHs)Co2
(CL)2NH(CJ(e)), N-n-butylaminoethyl methacrylate (,0(2=C(CL)C0
,2(CH2)2NH(CH2person plate,),2-aminoethylmethacrylate((&=C(CHs)CO2(
CHJ2Nl&→, 3-amino-1-globilmethacυ
rate, (c:n.

=C((?f-I3)Cot(CH2),NH2),
4-Amino/-1-butyl methacrylate (value = C<C) CO, (C)N, 6-amino-1-hexyl methacrylate CCH2=C(C) C07 (CH2)
6NH2) and any one of the compounds (m) according to the above general formula were used to carry out the same reaction as in formula (7), resulting in either compound (IV) or (
A compound (■) having a structure similar to V), that is, a compound represented by the general formula of the present invention was obtained.

That is, compound (Il[) and compound (Vl)'e (
It was revealed that the compound (■) was produced when the reaction was carried out in the same manner as in formula 7).

0 (cH,)n NR'2 (V[) CHs (&=C R/ o - (■) (However, in the formula, R' is -H, CmH2m++ s m +
(n represents an integer) Next, the compound (1'/)4f and N,N/-methylenebisacrylamide 0.2r'116d was dissolved in water and filtered, and this solution was degassed under reduced pressure and spun onto a glass substrate. Coded. When the obtained film was irradiated with ultraviolet light from a mercury lamp (250 W) for 3 hours, a strong heavy gold film was obtained.

On the other hand, this compound CM) 15 f was dissolved in 100-methyl alcohol, 0.15 f of 2,2'-azobisisobutyronitrile (AIBN) was added as a reaction initiator, and the mixture was reacted at 70°C for 15 hours. Ta. After the reaction was completed, the solution was poured into a large excess of acetone, the solution was allowed to stand still, the supernatant liquid was discarded, and the residue was collected. After repeating the same operation three times, the remaining liquid was dissolved in methyl alcohol, filtered using absorbent cotton, the filtrate was added dropwise to a large excess of acetone with stirring, and the supernatant liquid was left to stand, the supernatant liquid was discarded, and the product When dried under vacuum, the yield was 70%.

The molecular weight of this product was about 1oooo, but as a result of infrared spectroscopy, the peak around 1 620 cm, which corresponds to the c=c bond characteristic of methacrylate, had disappeared.
It was confirmed that it is a polymer.

This Polymer 3f was dissolved in 20i of water, spin-coded onto a glass substrate, and dried at 60'C for 2 hours, resulting in a transparent and uniform film.

Next, the above compound (IV) 2.5 f and N , N
'-methylenebisacrylamide 0.125 r'k,
The solution was dissolved in boiled pure water at room temperature, filtered, placed in a reaction vessel, and diluted with boiled pure water to make a total of 50 CJ. After degassing this solution under reduced pressure, β-dimethylamizolobionitrile 05- and beroxonisulfate ammonium 0.05-
After adding f with gentle stirring, the reaction container was heated to 50°C.
When the mixture was heated to ℃ and allowed to stand for 2 hours, dal was formed.

Furthermore, when the same reaction as above was carried out using the compound (■) according to the above general formula, a polymer film or dull was obtained in each case. That is, the above compound (■) according to the present invention
It was clear that the compound polymerized easily like known hydrophilic acrylic monomers and formed a strong film or dull layer.

For comparison, similar film formation was attempted using the naturally occurring phospholipids phos-7atysolethanolamine and phosphatitulcholine, but a uniform film could not be obtained and the resulting film was very thin. It was weak.

(Effects of the Invention) As is clear from the above explanation, according to the present invention, a polymer having a phospholipid structure can be easily produced in a few reaction steps by passing through an intermediate that can be considered as a precursor as shown in the previous author. It can be synthesized with high yield and reactivity, and can be produced economically and at low cost on an industrial scale.

The above-mentioned phospholipid-like structure polymer according to the present invention has properties not found in conventional natural phospholipids, namely, because it is a polymer, it is extremely easy to form a membrane.
Moreover, the resulting membrane is much stronger than that of natural phospholipids. Therefore, the humidity sensor, gas sensor,
It has great industrial value as it can be used in a wide range of fields such as ion-permeable membranes, artificial organs, cell fusion, fermentation fixation, biosensors, and artificial cultivation.

[Brief explanation of drawings]

The drawing shows the results of infrared spectroscopic analysis of an example of the compound of the present invention. Procedural amendment dated January 25, 1980, Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office, Minor Case Indication Patent Application No. 73959 No. 2 issued in 1982.
(D name, 6. Products and polymers with lipid-like structure and their manufacturing method 3, Relationship with the person making the amendment case Clock Applicant (029) Oki Electric Industry Co., Ltd. (2 others) 4, Agent 5, date of amendment order Showa year, month, day (self-A
) 6. Detailed description of the invention in the specification to be amended, Drawing 7, Contents of the amendment as shown in attached sheet 7 Contents of the amendment 1) Description, page 5, line 8 [Commum, 3. J to [C
ommum. Correct it as Vol, 3, J. 2) On the same page 7, in the 3rd line from the bottom, "elementary analysis and" is corrected to "elementary analysis and". 3) Correct "same" to "same" in the 6th line from the bottom of page 9. 4) On page 9, in the 4th line from the bottom, ``1 type'' is corrected to ``1 type.'' 5) 4th line from the bottom of page 10 r (CL=C(CHs)COz(CHt)aN(CH
(CHs) bow r (CH2=C(CHs)CO2(
Correct it as CHJ2N(CH(CI(s)2)2)J. 6) On page 14, line 4, "beroxonisulfuric acid" is corrected to "beroxonisulfuric acid". 7) Delete "and reactivity" on page 15, lines 3 and 4. 8) Correct the drawing as shown in the attached sheet.

Claims (1)

[Claims] (1) General formula % Formula % Represents a substituent selected from the group consisting of -H, -CmH2m+1, where m and n represent integers. ) A compound having a phospholipid-like structure 'f: (2. A polymer having a phospholipid-like structure obtained by polymerizing the compound described in claim 1. (3) General formula and general formula Hs 0 (CH2)n NR'2 (both A general formula characterized by reacting a compound represented by the formula (where R and R' each represent a substituent selected from the same group of substituents as R and R' in formula (1)) in a solvent. , CH3 ■ CH2=C CmOR' 0 1 1 1 (0(CHJn N'' CH2CH20P OR1 R'0-) A method for producing a compound having a phospholipid-like structure.