JP4996575B2 - ニトロンの製造 - Google Patents
ニトロンの製造 Download PDFInfo
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- JP4996575B2 JP4996575B2 JP2008266075A JP2008266075A JP4996575B2 JP 4996575 B2 JP4996575 B2 JP 4996575B2 JP 2008266075 A JP2008266075 A JP 2008266075A JP 2008266075 A JP2008266075 A JP 2008266075A JP 4996575 B2 JP4996575 B2 JP 4996575B2
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- carbon atoms
- alkyl group
- tert
- formula
- butyl
- Prior art date
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- CWGBFIRHYJNILV-UHFFFAOYSA-N (1,4-diphenyl-1,2,4-triazol-4-ium-3-yl)-phenylazanide Chemical compound C=1C=CC=CC=1[N-]C1=NN(C=2C=CC=CC=2)C=[N+]1C1=CC=CC=C1 CWGBFIRHYJNILV-UHFFFAOYSA-N 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 title description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 150000002466 imines Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 15
- 150000004965 peroxy acids Chemical class 0.000 claims description 15
- -1 tert- octyl Chemical group 0.000 claims description 14
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 claims description 13
- 239000011541 reaction mixture Substances 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000295 fuel oil Substances 0.000 claims description 4
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 239000010687 lubricating oil Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 4
- 150000007513 acids Chemical group 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 16
- 150000001412 amines Chemical class 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- DOZRDZLFLOODMB-UHFFFAOYSA-N 3,5-di-tert-Butyl-4-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC(C=O)=CC(C(C)(C)C)=C1O DOZRDZLFLOODMB-UHFFFAOYSA-N 0.000 description 12
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- 235000019439 ethyl acetate Nutrition 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000004566 IR spectroscopy Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- IYSYLWYGCWTJSG-XFXZXTDPSA-N n-tert-butyl-1-phenylmethanimine oxide Chemical compound CC(C)(C)[N+](\[O-])=C\C1=CC=CC=C1 IYSYLWYGCWTJSG-XFXZXTDPSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- QIJIUJYANDSEKG-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N QIJIUJYANDSEKG-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 150000003935 benzaldehydes Chemical class 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000003818 flash chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010747 number 6 fuel oil Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 0 *c1c(*)c(O)c(*)c(*)c1C=*[O-] Chemical compound *c1c(*)c(O)c(*)c(*)c1C=*[O-] 0.000 description 1
- JJULABXIXFRDCQ-UHFFFAOYSA-N 2,3,4-tritert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1C(C)(C)C JJULABXIXFRDCQ-UHFFFAOYSA-N 0.000 description 1
- RQPSVYAEBMSDIX-UHFFFAOYSA-N 2,6-ditert-butyl-4-(2,4,4-trimethylpentan-2-yliminomethyl)phenol Chemical compound CC(C)(C)CC(C)(C)N=CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 RQPSVYAEBMSDIX-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical group OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- SJGALSBBFTYSBA-UHFFFAOYSA-N oxaziridine Chemical compound C1NO1 SJGALSBBFTYSBA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
- C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/22—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms containing a carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/14—Containing carbon-to-nitrogen double bounds, e.g. guanidines, hydrazones, semicarbazones
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Lubricants (AREA)
Description
のニトロンの製造方法であって、式(II):
イミンの単離を伴う、2,6−ジ−tert−ブチル−4−(N−tert−オクチル)ニトロニルフェノール(DBONP)の製造
TEFLON被覆した磁気攪拌機、温度計、窒素ガス流、添加漏斗並びに凝縮器及び受器を取り付けたディーン・スターク(Dean−Stark)装置を取り付けた、窒素充填した250mLの四つ口丸底フラスコに、9.8590g(0.042モル)の3,5−ジ−t−ブチル−4−ヒドロキシベンズアルデヒドを添加し、続いて100mLのトルエンを、激しく撹拌しながら添加した。この溶液は透明ではなく、このアルデヒドは室温でトルエン中に溶解性ではなかった。この反応物の中に、添加漏斗を経て、5.8gのt−オクチルアミンを添加した。この反応フラスコを、加熱マントルによって60℃までゆっくり加熱し、温度を、THERM−O−WATCH(登録商標)コントローラー/モニターによって制御した。溶液は、透明な暗い赤色を帯びた褐色になった。薄層クロマトグラフィー(TLC)によって、この反応を60℃で2時間モニターした。次いで、温度を110℃まで上昇させて、トルエンとの共沸蒸留によって水を除去した。水とトルエンとの共沸混合物を、ディーン・スタークに取り付けた受器内に集めた。水の計算した量が除去された後、反応物を室温にまで冷却した。反応の完結は、赤外分光法(IR)分析により及びディーン・スターク受器内に集められた水の量によりモニターした。IR分析によって、波数1682cm−1(アルデヒドC=O)の消滅及び波数1621cm−1(イミンC=N)の出現が確認された。このイミンを、水吸引下でロータリーエバポレーターを使用してトルエンを蒸発させることによって、94.48%収率で得た。
(a)からの13.7g(0.0396モル)の2,6−ジ−tert−ブチル−4−((2,4,4−トリメチルペンタン−2−イルイミノ)メチル)フェノールを、温度計、凝縮器及び圧力平衡アームを有する添加供給漏斗を取り付けた、500mLの三つ口丸底フラスコに添加した。100mLの塩化メチレンをこのフラスコに添加して、イミンを溶解させた。100mLの酢酸エチル中の、10.18gの精製したメタ−クロロペルオキシ安息香酸(市販のMCPBAは、典型的には、70〜77%純度である。不純物は、過酸よりも一層酸性であるm−クロロ安息香酸である。従って、MCPBAは、pH7.5のリン酸塩緩衝液で洗浄することによって精製し、減圧下で乾燥する)の溶液を、ビーカー内で製造し、供給漏斗内に移した。反応フラスコを、氷浴を使用して0℃まで冷却した。温度が0℃に達したとき、供給漏斗からのMCPBAの溶液を、反応フラスコ内に、45〜60分間かけてゆっくり供給し、その間、温度を0℃に維持した。この反応混合物は、色が最初は青みに変わり、最終的に緑色に変化した。この反応混合物を0℃で2時間保持し、次いで室温にまでゆっくり加温した。この反応混合物を1リットルの分液漏斗に移した。次いで、この混合物を、100mLの7%NaHCO3溶液で2回洗浄し、続いて、それぞれ100mLの水で2回、洗浄した。次いでこの混合物を、100mLの飽和塩化ナトリウム溶液で2回洗浄し、続いて100mLの水で2回洗浄した。次いで、この混合物を、Na2SO4又はMgSO4を使用して一晩乾燥した。次いで、粗製ニトロンを、ロータリーエバポレーターを使用して濃縮した。このニトロンを、シリカゲル(66Å)を使用するフラッシュクロマトグラフィーカラムを使用して精製し、生成物をヘキサン/酢酸エチル(「EtOAc」)(70:30)の混合物で溶離して、13.56gの黄色みを帯びた固体結晶を得た。この最終生成物をペンタンで再結晶して、12.1gの灰白色結晶性固体を得た。この融点は150〜155℃であった。
イミンの単離を伴わない(DBONP)の製造
TEFLON被覆した磁気攪拌機、温度計、窒素ガス流、添加漏斗並びに凝縮器及び受器を取り付けたディーン・スターク装置を取り付けた、窒素充填した250mLの四つ口丸底フラスコに、9.8590g(0.042モル)の3,5−ジ−t−ブチル−4−ヒドロキシベンズアルデヒドを添加し、続いて100mLのトルエンを、激しく撹拌しながら添加した。この溶液は透明ではなく、このアルデヒドは室温でトルエン中に溶解性ではなかった。この反応物の中に、添加漏斗を経て、5.8gのt−オクチルアミンを添加した。この反応フラスコを、加熱マントルによって60℃までゆっくり加熱し、温度を、THERM−O−WATCH(登録商標)コントローラー/モニターによって制御した。溶液は、透明な暗い赤色を帯びた褐色になった。薄層クロマトグラフィー(TLC)によって、この反応を60℃で2時間モニターした。次いで、温度を110℃まで上昇させて、トルエンとの共沸蒸留によって水を除去した。水とトルエンとの共沸混合物を、ディーン・スターク装置に取り付けた受器内に集めた。水の計算した量が除去された後、反応物を室温にまで冷却した。反応の完結は、赤外分光法(IR)分析により及びディーン・スターク受器内に集められた水の量によりモニターした。IR分析によって、波数1682cm−1(アルデヒドC=O)の消滅及び波数1621cm−1(イミンC=N)の出現が確認された。ディーン・スターク装置、凝縮器及び受器を取り外した。
Claims (9)
- Rが、第三級であり、かつ8〜22個の炭素原子を有し、ペルオキシ酸が、ペルオキシ安息香酸又はアルキル基、ニトロ基、アルコキシ基、もしくはハロゲンによって置換されたペルオキシ安息香酸である、請求項1記載の方法。
- Rがtert−オクチルであり、R3及びR4がtert−ブチルであり、R1及びR2が水素であり、ペルオキシ酸がメタ−クロロペルオキシ安息香酸である、請求項2記載の方法。
- 反応混合物を、30℃より高い温度まで加熱しない、請求項3記載の方法。
- Rが、第三級であり、かつ8〜22個の炭素原子を有する、請求項5記載の方法。
- Rがtert−オクチルである、請求項6記載の方法。
- R3及びR4がtert−ブチルである、請求項8記載の化合物。
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