CN117142932A - 一种金属钐促进下银催化合成醛的方法 - Google Patents
一种金属钐促进下银催化合成醛的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 29
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052772 Samarium Inorganic materials 0.000 title claims abstract description 16
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 11
- 230000002194 synthesizing effect Effects 0.000 title claims description 10
- 230000001737 promoting effect Effects 0.000 title claims description 4
- 238000006555 catalytic reaction Methods 0.000 title description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title description 2
- 229910052709 silver Inorganic materials 0.000 title description 2
- 239000004332 silver Substances 0.000 title description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 6
- 150000005826 halohydrocarbons Chemical class 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 238000005580 one pot reaction Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 2
- 229930195733 hydrocarbon Natural products 0.000 claims 2
- 150000002430 hydrocarbons Chemical class 0.000 claims 2
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000012043 crude product Substances 0.000 abstract description 3
- 239000011541 reaction mixture Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
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- 150000001299 aldehydes Chemical class 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- -1 aldehyde compound Chemical class 0.000 description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- UAWABSHMGXMCRK-UHFFFAOYSA-L samarium(ii) iodide Chemical compound I[Sm]I UAWABSHMGXMCRK-UHFFFAOYSA-L 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000006170 formylation reaction Methods 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 230000022244 formylation Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 150000002192 fatty aldehydes Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
本发明公开了一种在N,N‑二甲基甲酰胺中用卤代烃在金属钐和银盐促进下来制备醛的简便方法。搅拌下将卤代烃加入N,N‑二甲基甲酰胺中,然后依次加入金属钐粉、银盐粉末。反应体系在无水的条件下进行。室温搅拌下直至反应完全。所得到的反应混合液进行溶剂回收。粗产物经柱色谱分离并蒸馏除去溶剂得到醛,产率60‑95%。
Description
技术领域
本发明属于有机化学合成领域,具体涉及一种使用金属钐促进下银盐催化由卤代烃在N,N-二甲基甲酰胺中一步合成醛的方法。
背景技术
醛类化合物无论作为溶剂、精细化工产品、基本化工原料还是有机合成试剂都具有广泛的应用。例如,在有机合成领域具有极其重要的应用。它通过催化加氢或与有机金属试剂加成,是获得醇类结构的重要方法,醛通过胺化还原可以得到胺类化合物[文献1.Cantu,D.C.;Padmaperuma,A.B.;Nguyen,M.-T.;et al,ACS Catal.2018,8(8),7645-7658l;文献2.Irrgang,T.;Kempe,R.,Chem.Rev.2020,120(17),9583-9674],醛类化合物在手性合成中也有广泛的应用[文献3.Marcum,J.S.;Meek,S.J.,J.Am.Chem.Soc.2022,144(42),19231-19237]。此外,醛还可以通过脱羰反应用于制备烯烃[文献4.Ainembabazi,D.;Reid,C.;Chen,A.;et al,J.Am.Chem.Soc.2020,142(2),696-699]。
关于醛类化合物的制备方法很多。其中,很早就发现的由醇类化合物的氧化制备醛的方法,至今仍有较多的研究和应用[文献5.Yan,Q.;Fang,Y.C.;Jia,Y.X.;et al,NewJ.Chem.2017,41(6),2372-2377;文献6.Wang,L.-Y.;Li,J.;Lv,Y.;et al,J.Organomet.Chem.2011,696(20),3257-3263]。这种方法需要耐氧化性能的设备,通常也会产生较多的工业排废。相对来说,烯烃的甲酰化策略是化工生产中制备醛类化合物比较广泛的工艺,该方法通过过渡金属催化将烯烃与一氧化碳和氢气进行甲酰化反应从而生成增加一个碳原子的醛[例如,文献7.Fleischer,I.;Wu,L.;Profir,I.;et alChem.Eur.J.2013,19(32),10589-10594]。这种工艺方法在反应过程中排废较少,但需要在较高压力下利用合成气(CO/H2)进行气相反应,对设备要求较高,所得产物的化学选择性和区域选择性也不易控制。此外,还可以通过羧酸衍生物的还原来制备醛[文献8.Rysak,V.;Descamps-Mandine,A.;Simon,P.;et al,Catal.Sci.Technol.2018,8(14),3504-3512],等等。这些合成方法原料不同,方法各异,反应路线所适用的条件和环境也各有区别,在化工生产和有机合成等领域均得到了广泛的应用。
从卤代烃出发,在丁基锂存在下与N,N-二取代甲酰胺反应制备醛类化合物,是一种比较独特的方法。该方法通过丁基锂与卤代烃发生的锂卤交换,并进一步与二取代甲酰胺发生甲酰化反应,从而直接在卤素位形成醛基[文献9.Gallou,Fabrice;Haenggi,Ruedi;Hirt,Hans;et al,Tetrahedron Lett.,2008,49(34),5024-5027]。由于卤代烃是常用的有机合成基本原料,因此该方法在应用上具有非常好的潜在价值。然而,由于丁基锂遇空气、湿气等极度敏感,是极度易燃易爆的危险试剂,且反应过程往往需要低温进行,一般在-78℃或更低,致使无论反应操作过程还是试剂贮存都有苛刻的要求,很难扩大反应规模。因此,该方法目前一般只应用于实验室合成中。我们前期研究曾经发现,在碘化亚铜催化下,以卤代烃为原料,N,N-甲基甲酰胺(DMF)为溶剂,借助金属钐还原作用,能在温和条件下高产率得到醛类化合物[文献10.Xiao,S.;Liu,C.;Song,B.,et al,Chem.Commun.2021,57(50),6169-6172]。相比之下,该方法操作条件温和,试剂易于使用和贮存,产率高,具有较好的大规模制备前景。不过,该方法也存在较明显的局限性。一方面,该方法主要适用于卤代芳烃制备芳香醛,不能合成脂肪醛,这大大限制了实际应用范围;另一方面,所用碘化亚铜用量较大(摩尔比不小于10%),碘化物较为昂贵,使得大规模使用受限。此外,所需反应时间较长,至少4个小时以上,从而增加了工艺成本。
钐是稀土元素的一种。自从1980年由法国化学家Kagan首次把二碘化钐引入有机合成中以来,钐试剂在有机合成中得到了非常广泛的应用,它能促进多种类型的化学反应和官能团的转化,并且已被成功地应用于多种天然产物的合成[文献11.Szostak,M.;Fazakerley,N.J.;Parmar,D.;et al,Chem.Rev.2014,114,5959-6039]。不过,二碘化钐在使用中存在着一些不足之处,如对空气十分敏感,因而长期保存比较困难,一般是现用现制。另一方面,二碘化钐作为单电子转移试剂,在使用过程中只利用了一个电子。这些都限制了其在大规模制备上的应用。相比而言,金属钐在空气中较稳定,易于操作,价格也相对便宜,而且有更多的电子可以得到有效的利用。因此,直接把金属钐用于有机合成具有更好的前景。我国有丰富的稀土资源,占世界储量的90%以上,开发利用稀土资源具有重大意义。
本发明公开了一种以N,N-二甲基甲酰胺(DMF)为溶剂,在溴化银(或溴化钾和硝酸银)存在下使用金属钐直接促进卤代烃(包括卤代脂肪烃和卤代芳香烃)和DMF一步反应制备醛类化合物的方法,该方法尚未见有国内外文献报道。
发明内容
本发明的目的在于提供一种用卤代烃以DMF为溶剂在金属钐和银盐促进下来制备醛的简便方法。
本发明的技术方案如下:
在银盐存在下,使用金属钐将卤代烃、DMF在温和条件下还原偶联为醛,其反应通式如下式所示:
式中,X优选Br,I;R优选烷基,苯基;银盐优选溴化银,硝酸银+溴化钠,醋酸银。
本发明的技术方案如下:搅拌下将卤代烃加入在事先除水干燥的N,N-二甲基甲酰胺中,然后依次加入金属钐粉、银盐粉末。其中,钐粉用量为卤代烃用量的摩尔比0.5-5倍;溴化银用量为钐粉用量的摩尔比0.01-0.05倍;N,N-二甲基甲酰胺用量为卤代烃质量的5-50倍;反应体系在无水的条件下进行。
室温搅拌下直至反应完全。所得到的反应混合液进行溶剂回收,残留物经后处理后,色谱柱分离得到醛的纯品,产率60-90%。
本发明的优点和积极效果:本发明所得产物类型广泛,可以用于多种醛类结构的合成;本发明合成路线简单高效,只需通过一步反应即可得到醛,操作步骤少,无需分离中间体,极大地简化了操作要求;本发明反应条件易于实现,而且可以在空气中直接操作,避免了无氧、低温、高温、光照、生物催化等特殊要求;本发明的原料简单易得,所用卤代烃成本低廉,为基本化工产品;本发明所用催化剂银盐用量很小,最低只需1%即可实现反应;本发明所用金属钐为稀土金属,我国的稀土资源占世界首位,因此有效开发利用稀土金属对我国具有重大意义;本发明合成的醛类化合物产率高,后处理过程简单,产品后处理时易于分离;本发明中所用的溶剂N,N-二甲基甲酰胺可以充分回收套用,并由此使反应成本进一步下降。
具体实施方式
下列合成实例用来进一步说明本发明,但不意味着限制本发明。
实例1
向反应容器中依次加入0.3g新制的金属钐粉,溴化银0.01g,然后加入5mL无水N,N-二甲基甲酰胺,磁力搅拌。加入溴苯0.2mL,室温下反应液在1h内颜色变深,继续反应2h。加入5mL稀盐酸(2mol·L-1)终止反应,反应混合液经后处理得到粗产物,然后进一步通过色谱柱纯化,得到苯甲醛,产率89%。
无色油状物;1H NMR(500MHz,Chloroform-d)δ10.02(s,1H),7.88(m,2H),7.63(m,1H),7.53(m,2H)ppm;13C NMR(125MHz,Chloroform-d)δ192.4,136.4,134.4,129.7,129.0ppm.
实例2
按实例1方法,使用溴化钠和硝酸银代替溴化银(等摩尔量),得到苯甲醛,产率87%。
实例3
按实例1方法,使用醋酸银代替溴化银(等摩尔量),得到苯甲醛,产率86%。
实例4
按实例1方法,使用苄基溴代替溴苯,得到苯乙醛,产率81%。
无色油状物;1H NMR(500MHz,Chloroform-d)δ9.75(t,J=2.5Hz,1H),7.39-7.22(m,5H),3.69(d,J=2.5 Hz,2H)ppm;13C NMR(125 MHz,Chloroform-d):δ199.5,131.8,129.6,129.0,127.4,50.6 ppm。
Claims (6)
1.一种合成醛的简易方法,其特征在于在溴化银存在下,使用金属钐促进卤代烃在N,N-二甲基甲酰胺中一步反应制备醛,其制备过程包括如下步骤:
室温搅拌下将卤代烃在事先除水干燥的N,N-二甲基甲酰胺中混合均匀,然后依次加入金属钐粉、银盐粉末。室温搅拌直至反应完全。所得到的反应混合液进行溶剂回收,残留物经后处理后,色谱柱分离得到醛纯品。
2.根据权利要求1所述的一种合成醛的简易方法,其特征在于所采用钐粉用量为卤代烃用量的摩尔比0.5-5倍;银盐用量为钐粉用量的摩尔比0.01-0.05倍;N,N-二甲基甲酰胺用量为卤代烃质量的5-50倍。
3.根据权利要求1所述的一种合成醛的简易方法,其特征在于所使用的卤代烃为卤代脂肪烃、卤代芳香烃的一种或几种。
4.根据权利要求1所述的一种合成醛的简易方法,其特征在于所使用的卤代烃为氯代烃、溴代烃、碘代烃的一种或几种。
5.根据权利要求1所述的一种合成醛的简易方法,其特征在于所使用的银盐为溴化银、硝酸银+溴化钠、醋酸银的一种或几种。
6.根据权利要求1所述的一种合成醛的简易方法,其特征在于反应温度为室温,反应为一锅法一步反应,反应溶剂能够回收,反应产率60-90%。
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