CN112812027B - 一种甲氧基苯胺类化合物及其合成方法 - Google Patents
一种甲氧基苯胺类化合物及其合成方法 Download PDFInfo
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- -1 Methoxyaniline compound Chemical class 0.000 title abstract description 10
- 238000010189 synthetic method Methods 0.000 title description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- NSBIQPJIWUJBBX-UHFFFAOYSA-N n-methoxyaniline Chemical compound CONC1=CC=CC=C1 NSBIQPJIWUJBBX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 15
- 239000011941 photocatalyst Substances 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 150000007524 organic acids Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
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- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 claims description 2
- YOJKKXRJMXIKSR-UHFFFAOYSA-N 1-nitro-2-phenylbenzene Chemical group [O-][N+](=O)C1=CC=CC=C1C1=CC=CC=C1 YOJKKXRJMXIKSR-UHFFFAOYSA-N 0.000 claims description 2
- VJJRVNGOHNKPHB-UHFFFAOYSA-N 1-nitro-4-[(4-nitrophenyl)methoxymethyl]benzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1COCC1=CC=C([N+]([O-])=O)C=C1 VJJRVNGOHNKPHB-UHFFFAOYSA-N 0.000 claims description 2
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 claims description 2
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- KLLLJCACIRKBDT-UHFFFAOYSA-N 2-phenyl-1H-indole Chemical compound N1C2=CC=CC=C2C=C1C1=CC=CC=C1 KLLLJCACIRKBDT-UHFFFAOYSA-N 0.000 description 1
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- XCSGPAVHZFQHGE-UHFFFAOYSA-N alachlor Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl XCSGPAVHZFQHGE-UHFFFAOYSA-N 0.000 description 1
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- MCPLVIGCWWTHFH-UHFFFAOYSA-M disodium;4-[4-[[4-(4-sulfoanilino)phenyl]-[4-(4-sulfonatophenyl)azaniumylidenecyclohexa-2,5-dien-1-ylidene]methyl]anilino]benzenesulfonate Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)O)=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-M 0.000 description 1
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- CXJSOEPQXUCJSA-UHFFFAOYSA-N pyridaphenthion Chemical compound N1=C(OP(=S)(OCC)OCC)C=CC(=O)N1C1=CC=CC=C1 CXJSOEPQXUCJSA-UHFFFAOYSA-N 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
- C07C255/59—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
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Abstract
本发明主要涉及一种甲氧基苯胺的制备方法。本发明在光催化剂及蓝光促进下，氩气氛围中，实现硝基类化合物和甲醇生成一种甲氧基苯胺的技术方案。制备得到分子结构稳定，化学性质优良的产品及其附加产品，该方法中使用光催化剂、蓝光源,为甲氧基苯胺类化合物的合成提供了一条新的路径。具有反应条件温和、反应体系简单、反应设备较少、实验操作简便等特点。本发明的甲氧基苯胺衍生物及其合成方法，可用于染料、农药、医药、橡胶助剂等多个工业生产领域；特别适合一锅法高效选择性合成甲氧基苯胺类化合物的科学研究与开发利用。
Description
技术领域
本发明涉及一种甲氧基苯胺类化合物及其合成方法，属于有机合成领域。
背景技术
甲氧基苯胺及衍生物是一类重要的有机类化合物，苯胺在染料、香料、塑料、农药、医药、橡胶助剂等工业生产中发挥着重要作用。例如：染料工业中可用于制造酸性墨水蓝G、酸性媒介BS、活性艳红X-SB 和金光红等；农药工业中用于生产许多杀虫剂、杀菌剂如DDV、除草醚、毒草胺等；用于制造防老剂甲、防老剂丁、促进剂M及CA等橡胶助剂；也可作为医药磺胺药的原料，并可作为***中的稳定剂、汽油中的防爆剂；其它还可用作制造对苯二酚、2-苯基吲哚等。由苯胺可衍生N-烷基苯胺、烷基苯胺等，可作为杀菌剂敌锈钠、杀虫剂***磷、哒嗪硫磷，除草剂甲草胺等的中间体。迄今为止关于合成此类化合物的方法存在合成步骤复杂，原子经济性差且官能团兼容性局限大，往往需对起始原料预先功能化。
发明内容
因此，本发明的目的是提供一种甲氧基苯胺及其衍生物。
本发明的又一目的是提供一种甲氧基苯胺及其衍生物的合成方法，具有反应条件简单，操作方便的优点。
从而，本发明的一种甲氧基苯胺及其衍生物，它的通式为式Ⅰa或Ib：
其中
R选自氢原子、卤素基团、烷基、(杂)芳基、氰基、乙酰基、烷氧基。
本发明还提供一种合成甲氧基苯胺及其衍生物的方法，在光催化剂和蓝光照射下，包括以下步骤：
(I)在反应容器内加入硝基化合物，甲醇，还原剂，光催化剂，蒸馏水，有机溶剂以及有机酸；
(II)将反应物充分混合，在氩气保护下蓝光照射及加热进行反应；
(III)纯化得到产物。
优选地，本发明的方法，所述硝基化合物是选自C6-C12芳香化合物，其通式为IIa或IIb。
其中
R选自氢原子、卤素基团、烷基、(杂)芳基、氰基、乙酰基、烷氧基。
优选地，本发明的方法，所述硝基苯类化合物选自：4-溴硝基苯，硝基苯，4-硝基苯甲醚，4-硝基苯乙酮，4-氯硝基苯，4-硝基苯甲腈，2-甲基硝基苯，2-硝基联苯。
优选地，本发明的方法，所述还原剂选自：三苯基膦，三环己基膦中的一种。
优选地，本发明的方法，所述光催化剂为：Ir(ppy)3，Ir(dFCF3ppy)2(dtbbpy)PF6，4CzIPN，Rose Bengal， Ru(bpy)3·6H2O，Eosin Y中的一种。
优选地，本发明的方法，所述的有机酸为：TsOH·H2O，TFA，TfOH，CH3SO3H，CH3COOH中的一种。
优选地，本发明的方法，所述的有机溶剂为：DCM，MeCN，CHCl3，DCE，Acetone，1,4-Dioxane中的一种；所述水的用量为：0.1-0.5mL。
优选地，本发明的方法，所述反应容器的气氛为：氩气氛围；硝基类化合物与光催化剂与有机酸与还原剂的摩尔比1.0:0.01-0.05:0.6-1.2:2.0-3.0；反应温度为50℃-65℃；反应时长为24h-36h。
本发明相比现有技术所产生的有益效果：
(I)本发明在光催化剂和蓝光照射下，氩气氛围中，实现硝基类化合物和甲醇转化为一种甲氧基苯胺及其衍生物的技术方案，采用一步直接选择性的合成目标产物，克服了现有多步合成方法带来的人、财、物的巨大浪费问题，节约了大量的研究时间与缩短生产周期；(II)氩气氛围下，光催化剂和蓝光源实现硝基类化合物和甲醇化合物转化为一种甲氧基苯胺及其衍生物的技术方案，它具有反应体系简单，反应条件温和，用料来源广泛，产品附加值增加显著且可利用性高，具备可预见的市场商业化前景；(III)硝基类化合物和甲醇转化为一种甲氧基苯胺及其衍生物的技术方案，它工艺科学、合理，基团定位和选择性好，实验操作容易，反应步骤明显缩短，所需仪器设备少。(IV)本发明的甲氧基苯胺衍生物及其合成方法，可用于染料、农药、医药、橡胶助剂等多个工业生产领域；特别适合一锅法高效选择性合成甲氧基苯胺类化合物的科学研究与开发利用。
具体实施方式
现对本发明作进一步详细的说明。下式为简化的示意，仅以示意方式说明本发明的基本结构，因此其仅显示与本发明有关的构成。
实施例1-16
步骤1：将硝基化合物(具体物质见表1)和甲醇加入反应容器中，分别将还原剂(具体物质见表1)、光催化剂(具体物质见表1)、水(具体投料量见表1)、有机酸(具体物质见表1)、有机溶剂(具体物质见表1)加入反应容器中。
步骤2：将反应容器均匀加热(如油浴加热)至表1中所述的温度及在蓝光下照射，硝基类化合物和甲醇在溶剂中进行反应，并持续表1中所述的时间；需要说明的本反应气氛选择氩气保护。
步骤3：提纯步骤。
表1：实施例1-16中硝基类化合物与甲醇、还原剂、光催化剂、水、有机有机酸、有机溶剂(硝基化合物、光催化剂、有机酸和还原剂)的摩尔比、反应温度和反应时间。
*硝基类化合物、光催化剂、有机酸和还原剂的摩尔比。
将步骤3后反应容器内的物质进行转化率检测并进行核磁共振，部分实施例的结果如下：
实施例11产物的核磁数据如下：
1H NMR(400MHz,Chloroform-d)δ6.91–6.88(m,2H),6.58(d,J＝7.9Hz,1H),3.84(s,3H),3.78(br,2H)；13C NMR(100MHz,Chloroform-d)δ147.8,135.2,123.6,115.7,113.7,109.5,55.6.
实施例12产物的核磁数据如下：
1H NMR(400MHz,DMSO-d6)δ6.96(d,J＝2.5Hz,1H),6.77–6.71(m,3H),4.84(br,2H),3.64(s,4H)；13C NMR (100MHz,Chloroform-d)δ152.7,137.7,117.4,116.7,115.0,109.6,55.9.
实施例16产物的核磁数据如下：
1H NMR(400MHz,Chloroform-d)δ7.50–7.44(m,4H),7.39–7.35(m,1H),6.81–6.73(m,3H),3.79(s,3H),3.52 (br,2H)；13C NMR(100MHz,Chloroform-d)δ152.6,139.4,137.1,129.0,128.7,128.7,127.2,116.8,115.6,114.3, 55.7.
表2实施例1-16反应的转化率及产物
以上述依据本发明的理想实施例为启示，通过上述的说明内容，相关工作人员完全可以在不偏离本项发明技术思想的范围内，进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容，必须要根据权利要求范围来确定其技术性范围。
Claims (3)
1.一种甲氧基苯胺及其衍生物的方法，其特征在于，在光催化剂和蓝光照射下，包括以下步骤：
(I)在反应容器内加入硝基化合物，甲醇，还原剂，催化剂，蒸馏水，有机溶剂以及有机酸；
(II)将反应物充分混合，在氩气保护下蓝光照射及加热进行反应；
(III)纯化得到产物；
所述硝基化合物依次选自：4-溴硝基苯，硝基苯，4-硝基苯甲醚，4-硝基苯乙酮，4-氯硝基苯，4-硝基苯甲腈，2-甲基硝基苯，2-溴硝基苯，2-硝基联苯；
与所述硝基化合物对应生成的甲氧基苯胺及其衍生物的结构式依次为：
所述催化剂为：lr(ppy)3，lr(dFCF3ppy)2(dtbbpy)PF6，4CzlPN，Rose Bengal，Ru(bpy)3·6H2O，Eosin Y中的一种，
所述有机酸为：TsOH·H2O，TFA，TfOH，CH3SO3H，CH3COOH中的一种；所述还原剂选自：三苯基膦，三环己基膦中的一种，
所述有机溶剂为：DCM，MeCN，CHCl3，DCE，Acetone，1，4-Dioxane中的一种。
2.根据权利要求1所述的方法，其特征在于，所述蒸馏水的用量为：0.1-0.5mL。
3.根据权利要求1所述的方法，其特征在于，硝基类化合物与催化剂与有机酸与还原剂的摩尔比1.0∶0.01-0.05∶0.6-1.2∶2.0-3.0，反应温度为50℃-65℃；反应时长为24h-36h。
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