JP2016222553A - Purification method of 4-hydroxy benzoic acid long chain ester - Google Patents
Purification method of 4-hydroxy benzoic acid long chain ester Download PDFInfo
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- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 title claims abstract description 44
- 150000002148 esters Chemical class 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000000746 purification Methods 0.000 title claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 35
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 17
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 13
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 6
- SJNCMISSTSMUFF-UHFFFAOYSA-N hexadecyl 4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC=C(O)C=C1 SJNCMISSTSMUFF-UHFFFAOYSA-N 0.000 claims description 4
- -1 4-hydroxybenzoic acid ester Chemical class 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 229940078552 o-xylene Drugs 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 125000005274 4-hydroxybenzoic acid group Chemical group 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 description 35
- 238000004458 analytical method Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- AFZZYIJIWUTJFO-UHFFFAOYSA-N 1,3-diethylbenzene Chemical compound CCC1=CC=CC(CC)=C1 AFZZYIJIWUTJFO-UHFFFAOYSA-N 0.000 description 2
- DSNHSQKRULAAEI-UHFFFAOYSA-N 1,4-Diethylbenzene Chemical compound CCC1=CC=C(CC)C=C1 DSNHSQKRULAAEI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- TYWMIZZBOVGFOV-UHFFFAOYSA-N tetracosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCO TYWMIZZBOVGFOV-UHFFFAOYSA-N 0.000 description 2
- MXAXVJBDSGPAIZ-UHFFFAOYSA-N tetracosyl 4-hydroxybenzoate Chemical compound OC1=CC=C(C(=O)OCCCCCCCCCCCCCCCCCCCCCCCC)C=C1 MXAXVJBDSGPAIZ-UHFFFAOYSA-N 0.000 description 2
- WWRCMNKATXZARA-UHFFFAOYSA-N 1-Isopropyl-2-methylbenzene Chemical compound CC(C)C1=CC=CC=C1C WWRCMNKATXZARA-UHFFFAOYSA-N 0.000 description 1
- XCYJPXQACVEIOS-UHFFFAOYSA-N 1-isopropyl-3-methylbenzene Chemical compound CC(C)C1=CC=CC(C)=C1 XCYJPXQACVEIOS-UHFFFAOYSA-N 0.000 description 1
- NNOOSZUXECFEDH-UHFFFAOYSA-N OC1=CC=C(C(=O)OCCCCCCCCCCCCCCCCCCCCCCC)C=C1 Chemical compound OC1=CC=C(C(=O)OCCCCCCCCCCCCCCCCCCCCCCC)C=C1 NNOOSZUXECFEDH-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- RGJOGVBIFBEFMC-UHFFFAOYSA-N docosyl 4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C1=CC=C(O)C=C1 RGJOGVBIFBEFMC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- VZZSQCCQLQYYIQ-UHFFFAOYSA-N henicosyl 4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCCCCOC(=O)C1=CC=C(O)C=C1 VZZSQCCQLQYYIQ-UHFFFAOYSA-N 0.000 description 1
- SNYRYVGRFMTVGK-UHFFFAOYSA-N heptadecyl 4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCOC(=O)C1=CC=C(O)C=C1 SNYRYVGRFMTVGK-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JVWIKEKXXPEYCW-UHFFFAOYSA-N icosyl 4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCCCOC(=O)C1=CC=C(O)C=C1 JVWIKEKXXPEYCW-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RKYSGLYYPJTRCZ-UHFFFAOYSA-N nonadecyl 4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCCOC(=O)C1=CC=C(O)C=C1 RKYSGLYYPJTRCZ-UHFFFAOYSA-N 0.000 description 1
- ITYCRFXTOMEQFF-UHFFFAOYSA-N octadecyl 4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C1=CC=C(O)C=C1 ITYCRFXTOMEQFF-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
Abstract
Description
本発明は、４−ヒドロキシ安息香酸長鎖エステルの精製方法に関する。 The present invention relates to a method for purifying 4-hydroxybenzoic acid long chain esters.
４−ヒドロキシ安息香酸長鎖エステルは、水酸基と疎水基を有する構造を有し、その構造的特徴から、可塑剤、相溶化剤、界面活性剤などの用途が提案されている。 4-Hydroxybenzoic acid long-chain ester has a structure having a hydroxyl group and a hydrophobic group, and uses such as a plasticizer, a compatibilizing agent and a surfactant have been proposed because of its structural characteristics.
一般的に化合物のエステル化は、原料カルボン酸とアルコールとを、硫酸等のプロトン酸触媒の存在下で反応させ、得られた反応液から触媒と未反応のカルボン酸を除去し、必要により晶析や蒸留などの精製を行うことによって製造する方法が知られている（特許文献１）。 In general, esterification of a compound is performed by reacting a raw material carboxylic acid and an alcohol in the presence of a protonic acid catalyst such as sulfuric acid, and removing the catalyst and unreacted carboxylic acid from the resulting reaction solution, and if necessary, crystallizing. A method of producing by purification such as precipitation or distillation is known (Patent Document 1).
４−ヒドロキシ安息香酸のエステル化についても、同様に、酸触媒の存在下でアルコールと反応させることによって、４−ヒドロキシ安息香酸エステルを合成することが可能である。しかし、４−ヒドロキシ安息香酸を炭素原子数１６以上の長鎖脂肪族アルコールと反応させて、４−ヒドロキシ安息香酸長鎖エステルを製造しようとした場合、原料である４−ヒドロキシ安息香酸や触媒などが残存するため、高純度の目的物を得るためには精製操作が必要であった。 Similarly, regarding esterification of 4-hydroxybenzoic acid, 4-hydroxybenzoic acid ester can be synthesized by reacting with alcohol in the presence of an acid catalyst. However, when 4-hydroxybenzoic acid is reacted with a long-chain aliphatic alcohol having 16 or more carbon atoms to produce 4-hydroxybenzoic acid long-chain ester, 4-hydroxybenzoic acid as a raw material, catalyst, etc. Therefore, a purification operation was required to obtain a high-purity target product.
精製は、通常目的物を含む粗結晶を溶融した後、あるいは非水溶性溶媒で希釈した後、水またはアルカリ水で抽出するのが一般的である。しかしながら、未反応のカルボン酸および触媒等の不純物を含む４−ヒドロキシ安息香酸長鎖エステルの粗組成物について、水やアルカリ水を加えて抽出しようとしても、分液性が極めて悪いため抽出が困難であり、抽出した場合であっても収量や純度が低く、高純度の目的物が得られないという問題があった。 In the purification, it is general to extract the crude crystals containing the target product with water or alkaline water after melting or diluting with a water-insoluble solvent. However, it is difficult to extract a crude composition of 4-hydroxybenzoic acid long-chain ester containing impurities such as unreacted carboxylic acid and catalyst, by adding water or alkaline water, because the liquid separation property is extremely poor. Even when extracted, there is a problem that the yield and purity are low and a high-purity target product cannot be obtained.
本発明の目的は、４−ヒドロキシ安息香酸長鎖エステルの粗組成物から触媒や反応原料などの残存物を容易に除去することができ、高純度の４−ヒドロキシ安息香酸長鎖エステルを高収率で得られる精製方法を提供することにある。 The object of the present invention is to easily remove residues such as catalysts and reaction raw materials from a crude composition of 4-hydroxybenzoic acid long chain ester, and to produce high-purity 4-hydroxybenzoic acid long chain ester with high yield. It is to provide a purification method obtained at a rate.
本発明者らは、４−ヒドロキシ安息香酸長鎖エステルの精製方法について鋭意検討した結果、４−ヒドロキシ安息香酸長鎖エステルの粗組成物を、非極性溶媒とアルコールとの混合溶液に溶解させた後、晶析することによって、未反応のカルボン酸や触媒などを容易に除去し、高純度の４−ヒドロキシ安息香酸長鎖エステルが得られることを見出し、本発明を完成するに至った。 As a result of intensive studies on a method for purifying 4-hydroxybenzoic acid long chain ester, the present inventors dissolved a crude composition of 4-hydroxybenzoic acid long chain ester in a mixed solution of a nonpolar solvent and alcohol. Thereafter, by crystallization, unreacted carboxylic acid, catalyst and the like were easily removed, and it was found that high-purity 4-hydroxybenzoic acid long chain ester was obtained, and the present invention was completed.
すなわち本発明は、式（１）で表される４−ヒドロキシ安息香酸長鎖エステルを含む粗組成物を、非極性溶媒とアルコールとの混合溶液に溶解させる工程（以下、溶解工程と称する）、および得られた溶液を晶析する工程（以下、晶析工程と称する）を含む、４−ヒドロキシ安息香酸長鎖エステルの精製方法を提供する。
本発明によれば、原料カルボン酸やアルコールを含む４−ヒドロキシ安息香酸長鎖エステル粗組成物を、非極性溶媒とアルコールとの混合溶液に溶解させ、次いで得られた溶液を晶析することにより効率よく残存物を除去し、高純度の４−ヒドロキシ安息香酸長鎖エステルを得ることができる。 According to the present invention, a 4-hydroxybenzoic acid long chain ester crude composition containing raw material carboxylic acid and alcohol is dissolved in a mixed solution of a nonpolar solvent and alcohol, and then the resulting solution is crystallized. The residue can be efficiently removed and a high purity 4-hydroxybenzoic acid long chain ester can be obtained.
本発明において、式（１）で表される４−ヒドロキシ安息香酸長鎖エステルを含む粗組成物とは、目的物である式（１）で表される４−ヒドロキシ安息香酸長鎖エステル以外に、反応原料や触媒および反応副生物などの不純物を含む組成物を意味する。不純物の含有量は反応方法によっても異なるが、粗組成物中１〜２０重量％、好ましくは３〜１０重量％である。 In the present invention, the crude composition containing a 4-hydroxybenzoic acid long chain ester represented by the formula (1) is other than the 4-hydroxybenzoic acid long chain ester represented by the formula (1) which is the target product. It means a composition containing impurities such as reaction raw materials, catalysts and reaction by-products. The content of impurities varies depending on the reaction method, but is 1 to 20% by weight, preferably 3 to 10% by weight in the crude composition.
本発明において、目的物である式（１）で表される４−ヒドロキシ安息香酸長鎖エステルは、４−ヒドロキシ安息香酸と炭素原子数１６〜２４の脂肪族アルコール（以下、長鎖アルコールと称する場合もある）から成るエステルであり、具体的には、４−ヒドロキシ安息香酸ヘキサデシル、４−ヒドロキシ安息香酸ヘプタデシル、４−ヒドロキシ安息香酸オクタデシル、４−ヒドロキシ安息香酸ノナデシル、４−ヒドロキシ安息香酸イコシル、４−ヒドロキシ安息香酸ヘンイコシル、４−ヒドロキシ安息香酸ドコシル、４−ヒドロキシ安息香酸トリコシルおよび４−ヒドロキシ安息香酸テトラコシルから選択される１種以上が挙げられる。これらの中でも、４−ヒドロキシ安息香酸ヘキサデシルが好ましい。 In the present invention, 4-hydroxybenzoic acid long-chain ester represented by the formula (1), which is the target product, is 4-hydroxybenzoic acid and an aliphatic alcohol having 16 to 24 carbon atoms (hereinafter referred to as long-chain alcohol). In particular, hexadecyl 4-hydroxybenzoate, heptadecyl 4-hydroxybenzoate, octadecyl 4-hydroxybenzoate, nonadecyl 4-hydroxybenzoate, icosyl 4-hydroxybenzoate, One or more types selected from henicosyl 4-hydroxybenzoate, docosyl 4-hydroxybenzoate, tricosyl 4-hydroxybenzoate and tetracosyl 4-hydroxybenzoate can be mentioned. Among these, hexadecyl 4-hydroxybenzoate is preferable.
粗組成物中に含まれる具体的な不純物としては、原料である４−ヒドロキシ安息香酸、触媒などの残存物のほか、反応副生物である長鎖アルコールの２量化エーテル体や硫酸エステルなどが挙げられる。 Specific impurities contained in the crude composition include 4-hydroxybenzoic acid as a raw material, a residue such as a catalyst, a dimerized ether form of a long-chain alcohol as a reaction by-product, and a sulfate ester. It is done.
４−ヒドロキシ安息香酸長鎖エステルの粗組成物を得る方法は特に限定されないが、触媒の存在下、４−ヒドロキシ安息香酸と炭素原子数１６〜２４の脂肪族アルコールとの反応によって得られたものを用いるのが良い。あるいは市販の低純度の４−ヒドロキシ安息香酸長鎖エステルを含む粗組成物を用いるのも良い。 The method for obtaining a crude composition of 4-hydroxybenzoic acid long chain ester is not particularly limited, but is obtained by reacting 4-hydroxybenzoic acid with an aliphatic alcohol having 16 to 24 carbon atoms in the presence of a catalyst. It is good to use. Alternatively, a crude composition containing a commercially available low-purity 4-hydroxybenzoic acid long chain ester may be used.
本発明の精製方法では、まず溶解工程において、４−ヒドロキシ安息香酸長鎖エステルの粗組成物を非極性溶媒とアルコールとの混合溶液に溶解させる。 In the purification method of the present invention, first, in the dissolution step, a crude composition of 4-hydroxybenzoic acid long chain ester is dissolved in a mixed solution of a nonpolar solvent and alcohol.
本発明で使用される非極性溶媒としては、ベンゼン、トルエン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン、エチルベンゼン、ｏ−ジエチルベンゼン、ｍ−ジエチルベンゼン、ｐ−ジエチルベンゼン、プロピルベンゼン、クメン、ｏ−シメン、ｍ−シメン、ｐ−シメン、ペンタン、ヘキサン、ヘプタン、オクタン、シクロペンタン、シクロヘキサン、シクロヘプタンおよびシクロオクタンからなる群から選択される１種以上が挙げられる。 Nonpolar solvents used in the present invention include benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, propylbenzene, cumene, o-cymene. , M-cymene, p-cymene, pentane, hexane, heptane, octane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane.
これらの中で、安全性および経済性に優れる点で、トルエン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン、ヘキサン、ヘプタン、オクタンおよびシクロヘキサンが好ましく、特に入手容易性および再結晶後の除去に優れることからトルエン、ヘプタンおよびヘキサンがより好ましい。 Of these, toluene, o-xylene, m-xylene, p-xylene, hexane, heptane, octane, and cyclohexane are preferable from the viewpoint of safety and economical efficiency, and particularly for easy availability and removal after recrystallization. Toluene, heptane, and hexane are more preferable because of their superiority.
また、本発明で使用されるアルコールとしては、メタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、２−ブタノール、ｔ−ブチルアルコール、２−メチル−１−プロパノール、エチレングリコール、プロピレングリコールおよびテトラメチレングリコールからなる群から選択される１種以上が挙げられる。 Moreover, as alcohol used by this invention, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 2-methyl-1-propanol, ethylene glycol, propylene glycol And one or more selected from the group consisting of tetramethylene glycol.
これらの中でも、安全性および経済性に優れる点で、メタノール、エタノール、１−プロパノール、２−プロパノールおよび１−ブタノールが好ましく、特に入手容易性および再結晶後の除去に優れることからメタノールおよび２−プロパノールがより好ましい。 Among these, methanol, ethanol, 1-propanol, 2-propanol and 1-butanol are preferable from the viewpoint of safety and economy, and methanol and 2-butanol are particularly easy to obtain and excellent in removal after recrystallization. More preferred is propanol.
非極性溶媒とアルコールとの比率については、用いる溶媒の種類によって異なるため特に限定されないが、混合溶液を基準とするアルコール比率が１０〜９０重量％、好ましくは２０〜８０重量％、より好ましくは３０〜７０重量％であるのが良い。アルコール比率が１０重量％を下回る場合、原料である４−ヒドロキシ安息香酸を除去することができない傾向があり、アルコール比率が９０重量％を上回る場合、原料である長鎖アルコールを除去することができない傾向がある。また、いずれの場合も次工程である晶析工程において撹拌が困難となる傾向がある。 The ratio of the nonpolar solvent to the alcohol is not particularly limited because it varies depending on the type of solvent used, but the alcohol ratio based on the mixed solution is 10 to 90% by weight, preferably 20 to 80% by weight, and more preferably 30%. It should be ~ 70% by weight. When the alcohol ratio is less than 10% by weight, the raw material 4-hydroxybenzoic acid tends to be unable to be removed. When the alcohol ratio exceeds 90% by weight, the raw material long-chain alcohol cannot be removed. Tend. In either case, stirring tends to be difficult in the next crystallization step.
本発明の精製方法において、４−ヒドロキシ安息香酸長鎖エステルの粗組成物と上記混合溶液との比率は、粗組成物に対して混合溶液１．２〜３倍重量、好ましくは１．５〜２倍重量であるのが良い。混合溶液の比率が１．２倍重量を下回る場合、原料や触媒あるいは副生物などの不純物が結晶中に取り込まれてしまい高純度の結晶を得ることが困難になる傾向があり、３倍重量を上回る場合、４−ヒドロキシ安息香酸長鎖エステルの収量が著しく減少する傾向がある。 In the purification method of the present invention, the ratio of the crude composition of 4-hydroxybenzoic acid long chain ester to the mixed solution is 1.2 to 3 times the weight of the mixed solution, preferably 1.5 to It should be twice the weight. If the ratio of the mixed solution is less than 1.2 times the weight, impurities such as raw materials, catalysts or by-products tend to be taken into the crystal and it becomes difficult to obtain high-purity crystals. If it exceeds, the yield of 4-hydroxybenzoic acid long chain ester tends to be significantly reduced.
溶解工程において、非極性溶媒とアルコールとの混合溶液の温度は、用いる非極性溶媒およびアルコールの種類および混合比率によって異なるため特に限定されないが、好ましくは３０℃〜６５℃、より好ましくは４０℃〜６０℃、さらに好ましくは４５℃〜５５℃である。 In the dissolution step, the temperature of the mixed solution of the nonpolar solvent and the alcohol is not particularly limited because it varies depending on the type and mixing ratio of the nonpolar solvent and the alcohol to be used, but is preferably 30 ° C to 65 ° C, more preferably 40 ° C to It is 60 degreeC, More preferably, it is 45 to 55 degreeC.
粗組成物が溶解した溶液は次いで晶析工程に供される。 The solution in which the crude composition is dissolved is then subjected to a crystallization process.
晶析工程は、好ましくは５〜３０℃、より好ましくは５〜２５℃、さらに好ましくは１０〜２０℃の温度下で攪拌しながら行われる。 The crystallization step is preferably performed at a temperature of 5 to 30 ° C, more preferably 5 to 25 ° C, and still more preferably 10 to 20 ° C with stirring.
晶析温度が５℃を下回る場合、原料や触媒あるいは副生物などの不純物が結晶中に取り込まれてしまい、高純度の結晶を得ることが困難になる。晶析温度が３０℃を上回る場合、４−ヒドロキシ安息香酸長鎖エステルの収量が減少する傾向がある。 When the crystallization temperature is lower than 5 ° C., impurities such as raw materials, catalysts or by-products are taken into the crystal, making it difficult to obtain a high-purity crystal. When the crystallization temperature is higher than 30 ° C, the yield of 4-hydroxybenzoic acid long chain ester tends to decrease.
晶析工程によって析出した結晶は濾過等の常套手段により固液分離し、目的物である４−ヒドロキシ安息香酸長鎖エステルを回収する。固液分離に際し、適宜有機溶媒を注いで結晶を洗浄するのが好ましい。固液分離の際に用いる有機溶媒としては、メタノール、エタノール、１−プロパノールおよび２−プロパノールからなる群から選択される１種以上が好ましく使用される。有機溶媒は、４−ヒドロキシ安息香酸長鎖エステル粗組成物に対し０．５〜２倍重量使用するのが好ましい。 Crystals precipitated in the crystallization step are subjected to solid-liquid separation by conventional means such as filtration, and the target 4-hydroxybenzoic acid long chain ester is recovered. In the solid-liquid separation, it is preferable to wash the crystals by appropriately pouring an organic solvent. As the organic solvent used in the solid-liquid separation, at least one selected from the group consisting of methanol, ethanol, 1-propanol and 2-propanol is preferably used. The organic solvent is preferably used in an amount of 0.5 to 2 times the weight of the crude 4-hydroxybenzoic acid long chain ester composition.
固液分離によって回収された結晶は、減圧下、５０℃未満の温度下で結晶状態のまま乾燥するか、あるいは５０℃以上に加熱して結晶を溶融させた後、溶媒を留去することによって、高純度の４−ヒドロキシ安息香酸長鎖エステルを得ることができる。 Crystals recovered by solid-liquid separation can be dried in a crystalline state under reduced pressure at a temperature below 50 ° C, or heated to 50 ° C or higher to melt the crystals, and then the solvent is distilled off. High purity 4-hydroxybenzoic acid long chain ester can be obtained.
以下、本発明を実施例により詳細に説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this.
［高速液体クロマトグラフィー（ＨＰＬＣ）］
装置： Ｗａｔｅｒｓ アライアンス ２４８７／２９９６
カラム型番： Ｌ−Ｃｏｌｕｍｎ
流量： １．０ｍＬ／分
溶媒比： Ｈ２Ｏ（ｐＨ２．３）／ＣＨ３ＯＨ＝５８／４２（３０分）→５分→１０／９０（５５分）、グラジエント分析
波長： ２２９ｎｍ／２５４ｎｍ
カラム温度： ４０℃
[High-performance liquid chromatography (HPLC)]
Equipment: Waters Alliance 2487/2996
Column model number: L-Column
Flow rate: 1.0 mL / min Solvent ratio: H 2 O (pH 2.3) / CH 3 OH = 58/42 (30 minutes) → 5 minutes → 10/90 (55 minutes), gradient analysis Wavelength: 229 nm / 254 nm
Column temperature: 40 ° C
［ガスクロマトグラフィー（ＧＣ）］
装置： 株式会社島津製作所製ＧＣ−２０１４／ＧＣ−１４Ａ
カラム型番: Ｇ−１００
注入量: １．０μＬ
オーブン温度: ３１０℃
キャリアガス: ヘリウム
検出器: ＦＩＤ
[Gas chromatography (GC)]
Equipment: GC-2014 / GC-14A manufactured by Shimadzu Corporation
Column model number: G-100
Injection volume: 1.0 μL
Oven temperature: 310 ° C
Carrier gas: Helium Detector: FID
参考例１（４−ヒドロキシ安息香酸ヘキサデシル粗組成物の調製）
攪拌機、温度センサーおよびディーンスターク装置を備えた５００ｍｌの４つ口フラスコに、ヘキサデカノール（ＣｅＯＨ）１２０．４ｇを投入、窒素気流下、７０℃まで昇温した。次いで、４−ヒドロキシ安息香酸（ＰＯＢ）７０．０ｇ、ｐ−トルエンスルホン酸一水和物２．３ｇおよび３０重量％次亜リン酸水溶液１．１ｇを加えて、一時間かけて１３０℃まで昇温し、同温度で８時間反応させた。得られた反応液（粗組成物）について、高速液体クロマトグラフィー（ＨＰＬＣ）およびガスクロマトグラフィー（ＧＣ）を用いて成分分析を行った。結果を表１に示す。
Reference Example 1 (Preparation of crude composition of hexadecyl 4-hydroxybenzoate)
To a 500 ml four-necked flask equipped with a stirrer, a temperature sensor, and a Dean-Stark apparatus, 120.4 g of hexadecanol (CeOH) was added, and the temperature was raised to 70 ° C. under a nitrogen stream. Next, 70.0 g of 4-hydroxybenzoic acid (POB), 2.3 g of p-toluenesulfonic acid monohydrate and 1.1 g of a 30 wt% aqueous hypophosphorous acid solution were added, and the temperature was raised to 130 ° C. over 1 hour. Warm and react for 8 hours at the same temperature. About the obtained reaction liquid (crude composition), component analysis was performed using high performance liquid chromatography (HPLC) and gas chromatography (GC). The results are shown in Table 1.
実施例１
攪拌機、温度センサーおよび冷却管を備えた１Ｌの４つ口フラスコに、非極性溶媒とアルコール（トルエン１９６ｇ、メタノール８４ｇ）を投入し、混合溶液を調製した。
そこに、１１０℃に冷却した参考例１の粗組成物１８０．７ｇを加えて、５０℃まで昇温して固形分を溶解させた後、１５℃まで冷却して結晶を析出させた。晶析時の攪拌状態は良好であった。ヌッチェを用いて結晶を吸引濾過した後、メタノール１４０ｇで洗浄し、４５℃、１０ｍｍＨｇの条件で乾燥させて結晶８４．１ｇを得た。
得られた結晶について、高速液体クロマトグラフィー（ＨＰＬＣ）およびガスクロマトグラフィー（ＧＣ）を用いて成分分析を行った。結果を表１に示す。
Example 1
A nonpolar solvent and alcohol (196 g of toluene, 84 g of methanol) were added to a 1 L four-necked flask equipped with a stirrer, a temperature sensor, and a condenser tube to prepare a mixed solution.
Thereto, 180.7 g of the crude composition of Reference Example 1 cooled to 110 ° C. was added, and the temperature was raised to 50 ° C. to dissolve the solid content, and then cooled to 15 ° C. to precipitate crystals. The stirring state during crystallization was good. The crystals were suction filtered using a Nutsche, washed with 140 g of methanol, and dried at 45 ° C. and 10 mmHg to obtain 84.1 g of crystals.
The obtained crystals were subjected to component analysis using high performance liquid chromatography (HPLC) and gas chromatography (GC). The results are shown in Table 1.
実施例２
混合溶液をトルエン１４０ｇおよびメタノール１４０ｇに変更したこと以外は実施例１と同様にして、結晶８５．７ｇを得た。得られた結晶の成分分析結果および攪拌状態を表１に示す。
Example 2
85.7 g of crystals were obtained in the same manner as in Example 1 except that the mixed solution was changed to 140 g of toluene and 140 g of methanol. Table 1 shows the component analysis results and stirring state of the obtained crystals.
実施例３
混合溶液をトルエン８４ｇおよびメタノール１９６ｇに変更したこと以外は実施例１と同様にして、結晶７９．８ｇを得た。得られた結晶の成分分析結果および攪拌状態を表１に示す。
Example 3
79.8 g of crystals were obtained in the same manner as in Example 1 except that the mixed solution was changed to 84 g of toluene and 196 g of methanol. Table 1 shows the component analysis results and stirring state of the obtained crystals.
実施例４
混合溶液をトルエン１９６ｇおよびエタノール８４ｇに変更したこと以外は実施例１と同様にして、結晶８１．０ｇを得た。得られた結晶の成分分析結果および攪拌状態を表１に示す。
Example 4
81.0 g of crystals were obtained in the same manner as in Example 1 except that the mixed solution was changed to 196 g of toluene and 84 g of ethanol. Table 1 shows the component analysis results and stirring state of the obtained crystals.
実施例５
混合溶液をトルエン１９６ｇおよび２−プロパノール８４ｇに変更したこと以外は実施例１と同様にして、結晶７７．２ｇを得た。得られた結晶の成分分析結果および攪拌状態を表１に示す。
Example 5
77.2 g of crystals were obtained in the same manner as in Example 1 except that the mixed solution was changed to 196 g of toluene and 84 g of 2-propanol. Table 1 shows the component analysis results and stirring state of the obtained crystals.
実施例６
混合溶液をトルエン１９６ｇおよびエチレングリコール８４ｇに変更し、乾燥温度を５５℃としたこと以外は実施例１と同様にして、結晶６９．９ｇを得た。得られた結晶の成分分析結果および攪拌状態を表１に示す。
Example 6
The mixed solution was changed to 196 g of toluene and 84 g of ethylene glycol, and 69.9 g of crystals were obtained in the same manner as in Example 1 except that the drying temperature was 55 ° C. Table 1 shows the component analysis results and stirring state of the obtained crystals.
実施例７
混合溶液をｎ−ヘキサン１９６ｇおよびメタノール８４ｇに変更したこと以外は実施例１と同様にして、結晶１２３．６ｇを得た。得られた結晶の成分分析結果および攪拌状態を表１に示す。
Example 7
Except having changed the mixed solution into 196g of n-hexane and 84g of methanol, it carried out similarly to Example 1, and obtained 123.6g of crystal | crystallizations. Table 1 shows the component analysis results and stirring state of the obtained crystals.
実施例８
混合溶液をｎ−ヘプタン１９６ｇおよび２−プロパノール８４ｇに変更したこと以外は実施例１と同様にして、結晶１２０．６ｇを得た。得られた結晶の成分分析結果および攪拌状態を表１に示す。
Example 8
120.6 g of crystals were obtained in the same manner as in Example 1 except that the mixed solution was changed to 196 g of n-heptane and 84 g of 2-propanol. Table 1 shows the component analysis results and stirring state of the obtained crystals.
比較例１
混合溶液をトルエン３６１．４ｇのみとしたこと以外は実施例１と同様にして、結晶６６．２ｇを得た。得られた結晶の成分分析結果および攪拌状態を表１に示す。
Comparative Example 1
66.2 g of crystals were obtained in the same manner as in Example 1 except that the mixed solution was only 361.4 g of toluene. Table 1 shows the component analysis results and stirring state of the obtained crystals.
比較例２
混合溶液をメタノール９０４ｇのみとし、昇温温度を６０℃としたこと以外は実施例１と同様にして、結晶６７．０ｇを得た。得られた結晶の成分分析結果および攪拌状態を表１に示す。
Comparative Example 2
67.0g of crystals were obtained in the same manner as in Example 1 except that the mixed solution was only 904g of methanol and the temperature elevation temperature was 60 ° C. Table 1 shows the component analysis results and stirring state of the obtained crystals.
参考例２（４−ヒドロキシ安息香酸テトラコシル粗組成物の調製）
ヘキサデカノールをテトラコサノール（ＴｃＯＨ）１７６．１ｇに変更したこと以外は参考例１と同様にして反応液（粗組成物）を得た。得られた粗組成物について、高速液体クロマトグラフィー（ＨＰＬＣ）およびガスクロマトグラフィー（ＧＣ）を用いて成分分析を行った。結果を表２に示す。
Reference Example 2 (Preparation of a crude composition of tetracosyl 4-hydroxybenzoate)
A reaction solution (crude composition) was obtained in the same manner as in Reference Example 1 except that hexadecanol was changed to 176.1 g of tetracosanol (TcOH). About the obtained crude composition, component analysis was performed using the high performance liquid chromatography (HPLC) and the gas chromatography (GC). The results are shown in Table 2.
実施例９
参考例２の粗組成物を用いたこと以外は実施例１と同様にして、結晶８１．３ｇを得た。得られた結晶の成分分析結果および攪拌状態を表２に示す。
Example 9
81.3 g of crystals were obtained in the same manner as in Example 1 except that the crude composition of Reference Example 2 was used. Table 2 shows the component analysis results and the stirring state of the obtained crystals.
比較例３
参考例２の粗組成物を用いたこと以外は比較例１と同様にして、結晶８１．３ｇを得た。得られた結晶の成分分析結果および攪拌状態を表２に示す。
Comparative Example 3
81.3 g of crystals were obtained in the same manner as in Comparative Example 1 except that the crude composition of Reference Example 2 was used. Table 2 shows the component analysis results and the stirring state of the obtained crystals.
表１および表２に示される通り、本発明によれば、４−ヒドロキシ安息香酸長鎖エステルの粗組成物から反応原料などの残存物が除去され、高純度の４−ヒドロキシ安息香酸長鎖エステルが高収率で得られる。 As shown in Table 1 and Table 2, according to the present invention, residues such as reaction raw materials are removed from the crude composition of 4-hydroxybenzoic acid long chain ester, and high purity 4-hydroxybenzoic acid long chain ester is removed. Is obtained in high yield.
Claims (8)
得られた溶液を晶析する工程
を含む、４−ヒドロキシ安息香酸長鎖エステルの精製方法。
A method for purifying 4-hydroxybenzoic acid long-chain ester, comprising a step of crystallizing the obtained solution.
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| US15/130,180 US9790165B2 (en) | 2015-04-30 | 2016-04-15 | Production process and purification process of 4-hydroxy-benzoic acid long chain ester |
| ES16166386.9T ES2643744T3 (en) | 2015-04-30 | 2016-04-21 | Production procedure and purification procedure of 4-hydroxybenzoic acid long chain ester |
| EP16166386.9A EP3088379B1 (en) | 2015-04-30 | 2016-04-21 | Production process and purification process of 4-hydroxy-benzoic acid long chain ester |
| TW105112803A TWI703125B (en) | 2015-04-30 | 2016-04-25 | Production process and purification process of 4-hydroxy-benzoic acid long chain ester |
| CN201610273034.7A CN106083593B (en) | 2015-04-30 | 2016-04-28 | Preparation method and purification method of 4-hydroxybenzoic acid long-chain ester |
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| JP2015107753A Active JP6518512B2 (en) | 2015-04-30 | 2015-05-27 | Purification method of 4-hydroxybenzoic acid long chain ester |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6272651A (en) * | 1985-09-27 | 1987-04-03 | Yoshitomi Pharmaceut Ind Ltd | P-hydroxybenzoic acid compound |
| JPH04327558A (en) * | 1991-04-25 | 1992-11-17 | Sumitomo Chem Co Ltd | Purification of bisphenol monoester |
| JPH0672960A (en) * | 1992-08-28 | 1994-03-15 | Yoshitomi Pharmaceut Ind Ltd | Production of granular beta-crystalline tetrakis(3-@(3754/24)3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl)methane |
| JPH06206849A (en) * | 1990-03-15 | 1994-07-26 | Consortium Elektrochem Ind Gmbh | Preparation of beta-resorcin phosphoric acid derivative |
| CN101982453A (en) * | 2010-09-10 | 2011-03-02 | 周峰岩 | Preparation method of nipagin ester compound under promotion of sulfonic acidic ionic liquid |
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2015
- 2015-05-27 JP JP2015107753A patent/JP6518512B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6272651A (en) * | 1985-09-27 | 1987-04-03 | Yoshitomi Pharmaceut Ind Ltd | P-hydroxybenzoic acid compound |
| JPH06206849A (en) * | 1990-03-15 | 1994-07-26 | Consortium Elektrochem Ind Gmbh | Preparation of beta-resorcin phosphoric acid derivative |
| JPH04327558A (en) * | 1991-04-25 | 1992-11-17 | Sumitomo Chem Co Ltd | Purification of bisphenol monoester |
| JPH0672960A (en) * | 1992-08-28 | 1994-03-15 | Yoshitomi Pharmaceut Ind Ltd | Production of granular beta-crystalline tetrakis(3-@(3754/24)3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl)methane |
| CN101982453A (en) * | 2010-09-10 | 2011-03-02 | 周峰岩 | Preparation method of nipagin ester compound under promotion of sulfonic acidic ionic liquid |
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| K.VOSSMANN ET AL.: "Preparation of lipophilic alkyl(hydroxy)benzoates by solvent-free lipase-catalyzed esterification an", APPL MICROBIOL BIOTECHNOL, vol. 80, JPN6018043715, 2008, pages 29 - 36, ISSN: 0003915540 * |
| KATSUMI NISHIMURA ET AL.: "Synthesis and DNA polymerase α and β inhibitory activity of alkyl p-coumarates and related compoun", CHEM.PHARM.BULL., vol. 57(5), JPN6018043718, 2009, pages 476 - 480, ISSN: 0003915541 * |
| M.DYMICKY ET AL.: "Inhibition of Clostridium by p-hydroxybenzoic Acid n-alkyl Esters", ANTIMICROBIAL AGENTS AND CHEMOTHERAPHY, vol. 15(6), JPN6018043712, 1979, pages 798 - 801, ISSN: 0003915539 * |
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