3634-83-1

Usage

Flammability and Explosibility

Nonflammable

Safety Profile

Moderately toxic by ingestion. A severe skin and eye irritant. A sensitizer. A flammable liquid. When heated to decomposition it emits very toxic fumes of NOx. See also ISOCYANATES.

InChI:InChI=1/C8H8N2O2/c11-9-5-7-2-1-3-8(4-7)6-10-12/h1-4H,5-6H2

Synthetic route

phosgene (75-44-5) + 1,3-di(aminomethyl)benzene (1477-55-0) → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
Stage #1: 1,3-di(aminomethyl)benzene With hydrogenchloride In water; 1,2-dichloro-benzene at 20℃; Autoclave; Large scale; Stage #2: phosgene In water; 1,2-dichloro-benzene at 145℃; for 2h; Autoclave; Large scale;	99.9%
With picoline In dichloromethane at -5 - 140℃; for 4h; Reagent/catalyst; Temperature;	98.3%
Stage #1: 1,3-di(aminomethyl)benzene With hydrogenchloride In chlorobenzene at 10℃; under 750.075 Torr; for 1.5h; Flow reactor; Large scale; Stage #2: phosgene In chlorobenzene at 131℃; under 750.075 Torr; for 3h; Temperature; Pressure; Solvent; Flow reactor; Large scale;	98.5%

diethyl 1,3-phenylenebis(methylene)dicarbamate (13406-38-7) → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
With zinc(II) oxide In 1,2-dichloro-benzene at 270℃; under 5625.56 Torr; for 2h; Temperature; Solvent; Reagent/catalyst; Pressure; Inert atmosphere; Sealed tube;	99.1%

1,3-bis-[(methoxycarbonylamino)-methyl]-benzene (54772-36-0) → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
With phthalic acid dimethyl ester; lead(II) acetate trihydrate; zinc(II) acetate dihydrate; sodium 4-dodecylbenzenesulfonate at 250℃; under 3750.38 Torr; for 0.333333h; Reagent/catalyst; Pressure; Inert atmosphere;	98.6%

1,3-di(aminomethyl)benzene (1477-55-0) + bis(trichloromethyl) carbonate (32315-10-9) → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
Stage #1: 1,3-di(aminomethyl)benzene With hydrogenchloride In chlorobenzene at 60 - 65℃; for 1h; Stage #2: bis(trichloromethyl) carbonate With hydrogenchloride; triphenylphosphine In chlorobenzene at 132℃; Solvent; Temperature;	94.8%
Stage #1: 1,3-di(aminomethyl)benzene With hydrogenchloride In water at 10 - 60℃; for 2h; Large scale; Stage #2: bis(trichloromethyl) carbonate In 1,2-dichloro-benzene at 130℃; for 28h; Temperature; Large scale;	94%
Stage #1: 1,3-di(aminomethyl)benzene With hydrogenchloride In water at 50℃; for 1h; Stage #2: bis(trichloromethyl) carbonate In 1,2-dichloro-benzene at 130℃; Temperature;	90%

silver (I) nitro cyanamide (20236-50-4) + 1,3-bis-(bromomethyl)benzene (626-15-3) → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
With magnesium sulfate In benzene at 80℃; for 3h;	94%

phosgene (75-44-5) → 3-chloromethylbenzyl isocyanate + m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
Stage #1: 1,3-di(aminomethyl)benzene With hydrogenchloride; 1,2-dichloro-benzene at 120℃; for 3 - 7h; Pressure between atmospheric and 0.05 MPa higher than atmospheric; Stage #2: phosgene In 1,2-dichloro-benzene at 160℃; for 6 - 8h; Product distribution / selectivity;	A n/a B 93.71%

C40H56N2O4 → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
With isocyanurate at 200 - 250℃; for 200h;	87%

[3-(Phenoxycarbonylamino-methyl)-benzyl]-carbamic acid phenyl ester (16578-54-4) → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
With DURANATE TPA-100 In 1,2-dichloro-benzene at 250℃; under 6000.6 Torr; for 200h; Inert atmosphere;	85%
In 1,2-dichloro-benzene at 160 - 250℃; under 6000.6 Torr; Inert atmosphere;	82%

phosgene (75-44-5) + Trimethylsilanyl-{3-[(trimethylsilanyl-amino)-methyl]-benzyl}-amine (54731-28-1) → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
In toluene

phosgene (75-44-5) + 1,3-Bis-(1,1,3,3-tetramethyl-disilazan-2-ylmethyl)-benzene (57586-52-4) → m-xylylene diisocyanate (3634-83-1)

1,3-di(aminomethyl)benzene (1477-55-0) + trichloromethyl chloroformate (503-38-8) → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
With pyrographite In ethyl acetate Heating;

1,3-di(aminomethyl)benzene (1477-55-0) + di-tert-butyl tricarbonate (24424-95-1) → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
In dichloromethane at 20℃; for 1h;

1,3-di(aminomethyl)benzene (1477-55-0) → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: H2SO4, (NH4)2SO4 2: toluene View Scheme
Multi-step reaction with 2 steps 1: H2SO4 View Scheme
Multi-step reaction with 2 steps 1.1: 12 h / 140 °C / 7500.75 - 60006 Torr / Autoclave 1.2: 10 h / 80 °C 2.1: 1,2-dichloro-benzene / 160 - 250 °C / 6000.6 Torr / Inert atmosphere View Scheme
Multi-step reaction with 2 steps 1.1: 12 h / 200 °C / 7500.75 - 60006 Torr / Autoclave 1.2: 10 h / 80 °C 2.1: 1,2-dichloro-benzene / 160 - 250 °C / 6000.6 Torr / Inert atmosphere View Scheme

N,N'-(1,3-phenylenebis(methylene))diformamide (59276-03-8) → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
In 1-Methylnaphthalene

m-xylylene bis(2,2,3,3-tetrafluoropropylcarbamate) (1338600-43-3) → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
at 200℃; under 7.05071 Torr;

m-xylylene bis(2,2,3,3-tetrafluoropropylcarbamate) (1338600-43-3) → C13H12F4N2O3 + m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
at 235℃;

C13H12F4N2O3 → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
Heating;

C18H27ClN2O4 → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: palladium on activated charcoal; sodium carbonate; hydrogen / 5 h / 90 °C / 3750.38 Torr / Autoclave 2: 200 - 300 °C / 100 Torr View Scheme

dibutyl (1,3-phenylenebis(methylene))dicarbamate → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
at 200 - 300℃; under 100 Torr;	51.9 g
at 200 - 300℃; under 100 Torr;	51.9 g

N,N'-meta-xylylene bis(N,N-diisobutylurea) → m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
at 200 - 300℃; under 100 Torr;	37.6 g
at 200 - 300℃; under 100 Torr;	37.6 g

1,3-di(aminomethyl)benzene (1477-55-0) + bis(trichloromethyl) carbonate (32315-10-9) → 3-chloromethylbenzyl isocyanate + 3-(dichloromethyl)benzylisocyanate + m-xylylene diisocyanate (3634-83-1)

Conditions	Yield
In 1,2-dichloro-benzene at 60 - 160℃; for 4h; Large scale;

m-xylylene diisocyanate (3634-83-1) → C10H10Cl2N2O2

Conditions	Yield
With hydrogenchloride In chlorobenzene at 30℃;	99%

m-xylylene diisocyanate (3634-83-1) + hydroxylauryl ether (209588-59-0) → Polymer, Mw 27300; Monomer(s): 13-oxapentacosane-1,25-diol; 1,3-bis(isocyanatomethyl)benzene

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 100℃; for 20h; Polymerization;	98%

methanol (67-56-1) + m-xylylene diisocyanate (3634-83-1) → 1,3-bis-[(methoxycarbonylamino)-methyl]-benzene (54772-36-0)

Conditions	Yield
With triethylamine 15 min, r.t., 30 min, reflux;	95%

5-amino-1H-imidazole-4-carboxamide monohydrochloride (72-40-2) + m-xylylene diisocyanate (3634-83-1) → 1,3-bis(5-amino-4-carbamoylimidazolecarboxamidomethyl)benzene

Conditions	Yield
With triethylamine In acetonitrile for 60h; Ambient temperature;	92%

m-xylylene diisocyanate (3634-83-1) + 3,3-bis(aminomethyl)-2,2′-dimethoxy-1,1′-binaphthalene (201138-33-2) → C34H32N4O4 (1474026-04-4)

Conditions	Yield
In chloroform for 2h; Reflux;	92%

m-xylylene diisocyanate (3634-83-1) + 6-[4-(6-hydroxy-hexyloxy)-phenoxy]-hexan-1-ol (154876-99-0) → Polymer, Mw 24900; Monomer(s): 1,4-bis(6-hydroxyhexyloxy)benzene; 1,3-bis(isocyanatomethyl)benzene

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 100℃; for 20h; Polymerization;	89%

m-xylylene diisocyanate (3634-83-1) + 4,6-diisopropyl-1,3-bis[methylene-(N'-2-aminophenylureylene)]-m-xylene (246018-53-1) → C38H44N8O4

Conditions	Yield
In N,N-dimethyl-formamide Cycloaddition;	85%

1-(4-nitrophenyl)-3-(2-amino-phenyl)urea (57709-67-8) + m-xylylene diisocyanate (3634-83-1) → 1,1'-(1,3-phenylenebis(methylene))bis(3-(2-(3-(4-nitrophenyl)ureido)phenyl)urea)

Conditions	Yield
In tetrahydrofuran for 4h; Reflux;	85%

(S)-2,2'-diamino-1,1'-binaphthalene (18531-95-8) + m-xylylene diisocyanate (3634-83-1) → (S)-N',N'''-(α,α'-m-xylenediyl)-[2,2'-bis(ureido)-1,1'-binaphthyl]

Conditions	Yield
In toluene for 5h; Inert atmosphere; Reflux;	83%

4,7,10-trioxa-1,13-diaminotridecane (4246-51-9) + m-xylylene diisocyanate (3634-83-1) → C22H36N4O6

Conditions	Yield
In N,N-dimethyl-formamide at 20℃; for 72h; Inert atmosphere; Cooling with ice;	78%

1,3-dimethanol benzene (626-18-6) + m-xylylene diisocyanate (3634-83-1) → 5,13-Diaza-3,15-dioxatricyclo<15.3.1.117,11>docosa-1(21),7,9,11(22),17,19-hexaene-4,14-dione

Conditions	Yield
With 1H-imidazole In toluene Heating;	77%
With triethylamine In tetrahydrofuran; toluene for 14h; Heating;	77%

1,8-diaminooctan (373-44-4) + m-xylylene diisocyanate (3634-83-1) → C18H28N4O2 (1092725-10-4)

Conditions	Yield
In N,N-dimethyl-formamide at 20℃; for 72h; Inert atmosphere; Cooling with ice;	75%

1-dicyanomethylene-5-(4-aminophenyl)indane (1290140-63-4) + m-xylylene diisocyanate (3634-83-1) → 1,3-bis[4-(1-dicyanomethyleneindan-5-yl)phenylureidomethyl]benzene (1290140-64-5)

Conditions	Yield
In chloroform at 20℃;	75%
In chloroform at 20℃; for 48h; Inert atmosphere;

3,6-dioxa-1,8-diaminooctane (929-59-9) + m-xylylene diisocyanate (3634-83-1) → C16H24N4O4 (1092725-06-8)

Conditions	Yield
In N,N-dimethyl-formamide at 20℃; for 72.5h; Inert atmosphere; Cooling with ice;	72%

4-vinyl benzylamine (1520-21-4) + m-xylylene diisocyanate (3634-83-1) → 1,1’-(1,3-phenylenebis(methylene))bis(3-(4-vinylphenyl)urea)

Conditions	Yield
In tetrahydrofuran at 20℃;	70%
In tetrahydrofuran at 20℃; Inert atmosphere;	70%

1 ,5-pentanediol (111-29-5) + m-xylylene diisocyanate (3634-83-1) → 5,11-Dioxa-3,13-diaza-bicyclo[13.3.1]nonadeca-1(18),15(19),16-triene-4,12-dione

Conditions	Yield
With triethylamine In tetrahydrofuran; toluene for 14h; Heating;	69%

2.6-bis(hydroxymethyl)pyridine (1195-59-1) + m-xylylene diisocyanate (3634-83-1) → 3,15-Dioxa-5,13,21-triaza-tricyclo[15.3.1.17,11]docosa-1(20),7,9,11(22),17(21),18-hexaene-4,14-dione

Conditions	Yield
With triethylamine In tetrahydrofuran; toluene for 14h; Heating;	68%

N,N'-dicyclohexyl-4-morpholine carboxamidine (4975-73-9) + m-xylylene diisocyanate (3634-83-1) → C44H70N8O4 (117688-76-3)

Conditions	Yield
In dichloromethane Ambient temperature;	65%

3α-amino-5β-colanato di metile (106697-49-8) + m-xylylene diisocyanate (3634-83-1) → bis[(24-methoxycarbonyl)-3-lithocholanyl]-N',N-xylene diurea

Conditions	Yield
In tetrahydrofuran at 20℃;	65%

C17H29NO4S + m-xylylene diisocyanate (3634-83-1) → C37H45N5O8S (870537-25-0)

Conditions	Yield
tin di(2-ethylhexanoate) In acetonitrile at 50℃; for 0.5h;	50%

Upstream product

• 75-44-5 phosgene 
• 1477-55-0 1,3-di(aminomethyl)benzene 
• 20236-50-4 silver (I) nitro cyanamide 
• 626-15-3 1,3-bis-(bromomethyl)benzene 
• 503-38-8 trichloromethyl chloroformate 
• 24424-95-1 di-tert-butyl tricarbonate 
• 13406-38-7 diethyl 1,3-phenylenebis(methylene)dicarbamate 
• 54772-36-0 1,3-bis-[(methoxycarbonylamino)-methyl]-benzene 
• 32315-10-9 bis(trichloromethyl) carbonate 
• 16578-54-4 [3-(Phenoxycarbonylamino-methyl)-benzyl]-carbamic acid phenyl ester 
• 59276-03-8 N,N'-(1,3-phenylenebis(methylene))diformamide 
• 57586-52-4 1,3-Bis-(1,1,3,3-tetramethyl-disilazan-2-ylmethyl)-benzene 
• 54731-28-1 Trimethylsilanyl-{3-[(trimethylsilanyl-amino)-methyl]-benzyl}-amine 
• 1338600-43-3 m-xylylene bis(2,2,3,3-tetrafluoropropylcarbamate) 

Downstream Products

• 54772-36-0 1,3-bis-[(methoxycarbonylamino)-methyl]-benzene 
• 124887-69-0 1,3-Bis<(1-carboxymethyl-3-hydantoinyl)methyl>benzene 
• 870537-25-0 C₃₇H₄₅N₅O₈S 
• 391894-58-9 C₁₈H₂₂N₄O₁₀ 
• 124887-70-3 1,3-Bis<(1-carboxymethyl-3-hydantoinyl)methyl>benzene dihydrate 
• 98128-51-9 Bis-(buta-1,3-dien-2-yl-methyl)-(m-xylylen)-dicarbamat 

Relevant academic research and scientific papers

METHOD FOR PRODUCING CARBAMATE AND METHOD FOR PRODUCING ISOCYANATE

The present invention provides a method for producing a carbamate that includes a step (1) and a step (2) described below: (1) a step of producing a compound (A) having a urea linkage, using an organic primary amine having at least one primary amino group per molecule and at least one compound selected from among carbon dioxide and carbonic acid derivatives, at a temperature lower than the thermal dissociation temperature of the urea linkage; and(2) a step of reacting the compound (A) with a carbonate ester to produce a carbamate.

Process of preparing isocyanate compounds comprising non-chlorination derivatives and Composition thereof

The present invention relates to a process for producing xylylene diisocyanate. The present invention relates to a process for preparing isocyanates comprising the obtained non-chlorinated derivatives. In particular, the present invention relates to an isocyanate composition comprising an unchlorinated derivative obtained by the reduction reaction and a polymerizable composition including the same.

Method for preparing high-purity m-xylylene diisocyanate from non-phosgene

The invention relates to the technical field of isocyanate preparation, in particular to a method for preparing high-purity m-xylylene diisocyanate from non-phosgene. The method for preparing the high-purity m-xylylene diisocyanate from the non-phosgene comprises the following steps: subjecting m-xylylenediamine and dimethyl carbonate to reacting under the action of a catalyst A to obtain methyl m-xylylene dicarbamate; and carrying out a decomposition reaction on methyl m-xylylene dicarbamate under the action of a catalyst B, emptying methanol through nitrogen replacement in the reaction process, and carrying out reduced-pressure distillation after the reaction is finished so as to obtain m-xylylene diisocyanate, wherein the catalyst A is a supported catalyst taking Lewis acid as an activecomponent and nano-SiO2 or nano-TiO2 as a carrier, and the catalyst B is an ultrafine composite oxide. The preparation method of the invention is good in product selectivity, high in yield, high in purity and free of catalyst residues, product quality is improved, and the requirements of high-end fields are met.

DIISOCYANATE COMPOSITION, PREPARATION METHOD THEREOF AND OPTICAL MATERIAL USING SAME

The diisocyanate composition according to an embodiment of the present invention comprises, in the composition, a benzyl isocyanate having a methyl group in an amount of 5 ppm to 200 ppm, an aromatic compound having a halogen group in an amount of 5 ppm to 1,000 ppm, a benzyl isocyanate having an ethyl group in an amount of 1 ppm to 1,000 ppm, or a combination thereof. It is possible to improve the optical characteristics by preventing the occurrence of yellowing, striae, and cloudiness and to enhance the mechanical properties such as impact resistance at the same time. Thus, it can be advantageously used to prepare an optical material of high quality.

METHOD OF PREPARING DIISOCYANATE COMPOSITION AND OPTICAL LENS

In the embodiments, an aqueous hydrochloric acid solution instead of hydrogen chloride gas and solid triphosgene instead of phosgene gas may be used in the process of preparing a diisocyanate from a diamine through a diamine hydrochloride. In addition, the embodiments provide processes for preparing a diisocyanate composition and an optical lens of higher quality, in which the reaction temperature of a diamine hydrochloride composition and triphosgene is controlled to a specific range, or a crude diisocyanate composition obtained from the reaction of a diamine hydrochloride composition and triphosgene is distilled at a specific temperature range, or the molar ratio of a diamine hydrochloride and triphosgene is adjusted to a specific range.

Construction of unsymmetrical bis-urea macrocyclic host for neutral molecule and chloride-ion binding

Construction of synthetic macrocyclic host that can bind with neutral molecules and anions has potential applications in supramolecular chemistry. Herein, we have designed and synthesized blue light emitting an unsymmetrical neutral bis-urea macrocyclic host. This macrocycle can bind with neutral DMF molecule (1:1) as well as Cl? ion (1:1) through noncovalent interactions. X-Ray crystal structure, 1H NMR titrations with Job's Plot, HRMS with isotropic distribution pattern, FT-IR, and density functional theory analysis revealed the binding of bis-urea macrocyclic host with the guest molecule.

METHOD OF PREPARING DIISOCYANATE COMPOSITION

In the embodiments, an aqueous hydrochloric acid solution instead of hydrogen chloride gas and solid triphosgene instead of phosgene gas may be used in the process of preparing a diisocyanate from a diamine through a diamine hydrochloride. In addition, the embodiments provide processes for preparing a diisocyanate composition and an optical lens, which are excellent in yield and quality with mitigated environmental problems by controlling the size of the diamine hydrochloride composition, the b* value according to the CIE color coordinate of the diamine hydrochloride composition, or the content of water in the diamine hydrochloride composition within a specific range.

METHOD OF PREPARING DIISOCYANATE COMPOSITION AND OPTICAL LENS

In the embodiments, an aqueous hydrochloric acid solution and an organic solvent instead of hydrogen chloride gas and solid triphosgene instead of phosgene gas may be used in the process of preparing a diisocyanate from a diamine through a diamine hydrochloride. In addition, the embodiments provide processes for preparing a diisocyanate composition and an optical lens, which are excellent in yield and quality with mitigated environmental problems by controlling the total content of metals, cations, or anions in a diamine hydrochloride composition.

Method for preparing low-chlorinated impurity content isocyanate based on salt formation light gasification (by machine translation)

The invention provides a method for preparing low-chlorinated impurity content isocyanate based on a salt-formation light gasification method. The proportion of the salt particle size distribution obtained by the salt formation reaction in the average particle size ±30% range is 70% or more, the average residence time without stirring is less than 60 min, and the product obtained by the method has lower chlorinated impurity content. (by machine translation)

Process of preparing isocyanate compounds comprising non-chlorination derivatives and Composition thereof

The present invention relates to a method for preparing isocyanates containing a non-chlorinated derivative obtained by converting a chlorinated derivative generated in a preparation process of xylylene diisocyanate into a non-chlorinated derivative by a reduction reaction. In particular, the present invention relates to an isocyanate composition comprising the non-chlorinated derivative obtained by the reduction reaction and a polymerizable composition comprising the same. The isocyanate composition is excellent in economic feasibility and easy to reduce chlorinated derivatives.COPYRIGHT KIPO 2021